POLYESTER BASED HYBRID ORGANIC COATINGS

A Dissertation
Presented to
The Graduate Faculty of The University of Akron




In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy





Xiaojiang Wang
August, 2012
ii

POLYESTER BASED HYBRID ORGANIC COATINGS


Xiaojiang Wang
Dissertation

Approved: Accepted:


Advisor Department Chair
Dr. Mark Soucek Dr. Robert Weiss

Committee Chair Dean of the College
Dr. Kevin Cavicchi Dr. Stephen Cheng

Committee Member Dean of the Graduate School
Dr. Thein Kyu Dr. George R. Newkome

Committee Member Date
Dr. Yi Pang

Committee Member
Dr. Matthew P. Espe

iii

ABSTRACT

Polyesters are a class of polymers widely used in organic coatings applications. In
this work, four types of organic coatings based on polyester polyols were prepared: UV-
curable polyester/poly(meth)acrylate coatings, thermal curable polyester polyurethane-
urea coatings, thermal curable non-isocyanate polyurethane coatings, and UV-curable
non-isocyanate polyurethane coatings.
Polyester/poly(meth)acrylate block copolymers are synthesized using a
combination of polycondensation and Atom-Transfer Radical Polymerization (ATRP).
All block copolymers are characterized by means of Nuclear Magnetic Resonance (NMR)
and Gel Permeation Chromatography (GPC). In the case of unsaturated-polyester-based
block copolymers the main chain double bond in the polyester backbone remains almost
unaffected during ATRP. The unsaturated block copolymers are crosslinkable and can
form networks upon photo-irradiation in the presence of a suitable photoinitiator. These
copolymers might be interesting candidates for coatings with better overall properties
than those based on neat polyesters.
Thermal curable polyester polyol based Polyurethane-Urea (PUU) coatings were
formulated using Partially Blocked HDI isocyanurate (PBH), Isophorone Diamine
(IPDA), and polyester polyol. As a comparison, the polyurethane coatings (PU) without
adding IPDA were also prepared. The mechanical and viscoelastic properties of the PUU
and PU coating were investigated by using tensile test and Dynamic Mechanical Thermal
iv

Analyzer (DMTA). It was found that PUU coating exhibited higher crosslink density, Tg,
tensile modulus and strength than the corresponding PU coating.
Thermal curable non-isocyanate polyurethane coatings were prepared by using
polyamine and cyclic carbonate terminated polyester. Cyclic carbonate terminated
polyester was synthesized from the reaction of the carbon dioxide and epoxidized
polyester which was prepared from the polyester polyol. The properties of the epoxidized
and cyclic carbonate terminated polyester were characterized by Brookfield viscometer,
NMR and Fourier Transform Infrared spectroscopy (FTIR).
UV-curable non-isocyanate polyurethane coatings were formulated by using
Acrylated Polyester (APE) oligomer and Non-isocyanate Urethane Dimethacrylates
(NUDMA) reactive diluents. The effect of the NUDMA on the viscosity of the APE
oligomer was investigated by Brookfield viscometer. The photopolymerization kinetics
of NUDMA reactive diluents were investigated by the real time FTIR. It was found that
the polymerization conversion and maximum polymerization rate increase with
increasing initiator concentration in the range from 0.5 % to 4.0 %. The formulation
system containing both the APE oligomer and NUDMA reactive dilutes showed higher
polymerization overall conversion and maximum polymerization rate than APE oligomer.
After UV curing, the viscoelastic, tensile and thermal properties of the cured films
were evaluated as a function of the reactive diluent by using DMTA, tensile test,
Differential Scanning Calorimeters (DSC), and Thermal Gravimetric Analysis (TGA). In
addition, coating properties such as pencil hardness, chemical resistance, impact
resistance, and gloss were also investigated. It was found that crosslink density, storage
and tensile modulus, pencil hardness, chemical resistance, gel content, total water
v

absorption, and Tg were directly proportional to amount of the reactive diluents.
Compared to the commercial Ethylene Glycol Dimethacrylate (EGDMA) reactive diluent,
the NUDMA reactive diluents show significant improvements in impact resistance and
elongation at break properties.

vi

ACKNOWLEDGMENTS

I would like to express my sincere gratitude and appreciation to my advisor, Dr.
Mark D. Soucek, for his invaluable guidance and continued encouragement throughout
this research.
I would like to extend my gratitude towards my committee members: Dr. Thein
Kyu, Dr. Kevin Cavicchi, Dr. Yi Pang, and Dr. Matthew P. Espe for their flexibility, time
and contribution.
I would also like to thank my labmates for their encouragement and help given to
me during my research work.
Finally, I would like to thank my family for their encouragement and support.


vii

TABLE OF CONTENTS

Page
LIST OF FIGURES .......................................................................................................... xii
LIST OF TABLES .......................................................................................................... xvii
CHAPTER
I. INTRODUCTION ........................................................................................................... 1
II. BACKGROUND ............................................................................................................ 5
2.1 Polyesters ................................................................................................................... 5
2.1.1 Polyesters history ................................................................................................. 5
2.1.2 Synthetic methods ................................................................................................ 7
2.1.3 Raw materials..................................................................................................... 12
2.1.4 Hydrolytic stability ............................................................................................ 15
2.1.5 Polyesters crosslinking mechanism ................................................................... 17
2.2 Hybrid polyesters ..................................................................................................... 20
2.2.1 Organic-Inorganic hybrid materials ................................................................... 20
2.2.2 Organic hybrid materials .................................................................................... 21
2.3 Atom Transfer Radical Polymerization (ATRP) ...................................................... 23
2.4 Polyurethane (PU) coatings ..................................................................................... 25
2.5 Non-isocyanate polyurethanes (NIPU) .................................................................... 28
viii

2.5.1 Mechanism for NIPU preparation ...................................................................... 29
2.5.2 Reactants for NIPU preparation ......................................................................... 31
2.5.3 Preparation of NIPU .......................................................................................... 34
III. POLYESTER/POLY(METH)ACRYLATE BLOCK COPOLYMERS BY
COMBINED POLYCONDENSATION/ATRP: CHARACTERIZATION AND
PROPERTIES ............................................................................................................. 40
3.1 Abstract .................................................................................................................... 40
3.2 Introduction .............................................................................................................. 40
3.3 Materials .................................................................................................................. 43
3.4 Instrumentation and characterization ....................................................................... 43
3.5 Synthesis .................................................................................................................. 45
3.5.1 Synthesis of IPAMA-HDNPG UPE ................................................................... 45
3.5.2 Synthesis of adipic acid/1,6-hexanediol (AA-HD) SPE .................................... 46
3.5.3 Synthesis of UPE-based difunctional macroinitiator (UPE1) for methacrylate
polymerization .................................................................................................... 47
3.5.4 Synthesis of UPE-based difunctional macroinitiator (UPE2) for acrylate
polymerization .................................................................................................... 47
3.5.5 Synthesis of poly(MMA)-block-UPE1-block-poly(MMA) (PMMA-b-UPE1-b-
PMMA) ............................................................................................................... 48
3.5.6 Synthesis of poly(BA)-block-UPE2-block-poly(BA) (PBA-b-UPE2-b-PBA) .. 49
3.5.7 Synthesis of poly(MMA)-block-poly(BA)-block-UPE2-block-poly(BA)-block-
poly(MMA) (PMMA-b-PBA-b-UPE2-b-PBA-b-PMMA) ................................ 49
3.5.8 Synthesis of poly(BA)-block-poly(MMA)-block-UPE1-block-poly(MMA)-
block-poly(BA) (PBA-b-PMMA-b-UPE1-b-PMMA-b-PBA) ........................... 50
3.5.9 Bulk ATRP of MMA using UPE-based macroinitiator ...................................... 50
3.5.10 Synthesis of poly(MMA)-block-SPE1-block-poly(MMA) (PMMA-b-SPE1-b-
PMMA) ............................................................................................................... 51
3.6 Results and discussion ............................................................................................. 52
ix

3.6.1 Synthesis of polyester-based block copolymers ................................................ 52
3.6.2 Synthesis of UPE-based block copolymers ....................................................... 55
3.6.3 Synthesis of SPE-based block copolymers ........................................................ 62
3.6.4 Glass transition temperatures of different polyester-based copolymers ............ 66
3.6.5 Network formation from unsaturated polyester-based block copolymers ......... 69
3.7 Conclusions .............................................................................................................. 70
IV. THERMAL CURABLE POLYURETHANE-UREA COATING BASED ON
POLYESTER POLYOLS ............................................................................................ 72
4.1 Abstract .................................................................................................................... 72
4.2 Introduction .............................................................................................................. 73
4.3 Materials .................................................................................................................. 76
4.4 Instrumentation and characterization ....................................................................... 76
4.5 Synthesis .................................................................................................................. 78
4.5.1 Synthesis of polyester polyol ............................................................................. 78
4.5.2 Synthesis of partially blocked HDI isocyanurate (PBH) ................................... 79
4.6 Coating formulation ................................................................................................. 80
4.7 Results ...................................................................................................................... 81
4.7.1 Preparation of partially blocked HDI isocyanurate (PBH) ................................ 82
4.7.2 Tensile properties ............................................................................................... 84
4.7.3 Viscoelastic properties ....................................................................................... 86
4.7.4 General coating properties ................................................................................. 89
4.8 Discussion ................................................................................................................ 90
4.9 Conclusions .............................................................................................................. 93
V. PREPARATION OF THE THERMAL CURABLE NON-ISOCYANATE
POLYURETHANE COATINGS ................................................................................ 94
x

5.1 Abstract .................................................................................................................... 94
5.2 Introduction .............................................................................................................. 94
5.3 Materials .................................................................................................................. 96
5.4 Characterization ....................................................................................................... 96
5.5 Synthesis .................................................................................................................. 97
5.5.1 Synthesis of hydroxyl terminated polyester (H-PE) .......................................... 97
5.5.2 Synthesis of epoxidized polyester (E-PE).......................................................... 97
5.5.3 Synthesis of cyclic carbonate polyester (CC-PE) .............................................. 98
5.5.4 Polyurethane preparation ................................................................................... 98
5.6 Results and discussion ............................................................................................. 98
5.7 Conclusions ............................................................................................................ 104
VI. PHOTOPOLYMERIZATION OF THE NON-ISOCYANATE URETHANE
DIMETHACRYLATES AS REACTIVE DILUENTS FOR UV-CURABLE
COATING ................................................................................................................. 105
6.1 Abstract .................................................................................................................. 105
6.2 Introduction ............................................................................................................ 106
6.3 Materials ................................................................................................................ 108
6.4 Instrumentation and characterization ..................................................................... 109
6.5 Synthesis ................................................................................................................ 109
6.5.1 Synthesis of non-isocyanate urethane diols ..................................................... 109
6.5.2 Synthesis of non-isocyanate urethane dimethacrylate ...................................... 111
6.5.3 Synthesis of the acrylated polyester (APE) oligomer .......................................112
6.6 Coating formulation ................................................................................................114
6.7 Results and discussion ............................................................................................115
6.7.1 Preparation of reactive diluents and oligomer ..................................................117
xi

6.7.2 Viscosity ........................................................................................................... 123
6.7.3 Kinetics studies by real-time FTIR .................................................................. 126
6.8 Conclusions ............................................................................................................ 133
VII. MECHANICAL AND FILM PROPERTY OF UV-CURABLE NON-ISOCYANATE
POLYURETHANE COATINGS .............................................................................. 135
7.1 Abstract .................................................................................................................. 135
7.2 Introduction ............................................................................................................ 136
7.3 Materials ................................................................................................................ 140
7.4 Instrumentation ...................................................................................................... 140
7.5 Synthesis ................................................................................................................ 141
7.5.1 Synthesis of the acrylated polyester (APE) oligomer ...................................... 141
7.5.2 Synthesis of non-isocyanate urethane dimethacrylate reactive diluents .......... 142
7.6 Coating formulation and evaluation ...................................................................... 144
7.7 Results .................................................................................................................... 146
7.7.1 Tensile properties ............................................................................................. 147
7.7.2 Viscoelastic properties ..................................................................................... 150
7.7.3 Thermal properties ........................................................................................... 154
7.7.4 Gel content properties ...................................................................................... 159
7.7.5 Water absorption properties ............................................................................. 160
7.7.6 General coating properties ............................................................................... 161
7.8 Discussion .............................................................................................................. 162
7.9 Conclusions ............................................................................................................ 167
VIII. CONCLUSIONS .................................................................................................... 169
REFERENCES ............................................................................................................... 172
xii

LIST OF FIGURES

Figure Page
2- 1 Polyester synthesis by direction polymerization ......................................................... 9
2- 2 Ester synthesis via acid chloride and alcohol reactions ............................................. 10
2- 3 Ester synthesis via acid and alcohol reaction by using N, N-
dicyclohexylcarbodiimide (DCC) as activating agent ....................................11
2- 4 Ester synthesis via epoxy-carboxyl reaction ..............................................................11
2- 5 Poly (-caprolactone) (PCL) synthesis via ring-opening polymerization (ROP) ...... 12
2- 6 The important polyols used for polyesters synthesis ................................................. 12
2- 7 The important polyacids used for polyesters synthesis ............................................. 13
2- 8 Ester group hydrolysis ............................................................................................... 16
2- 9 Diols with hydrophobic groups used in hydrolysis resistant polyester polyol
synthesis ........................................................................................................ 17
2- 10 Reaction between MF resins with acids .................................................................. 18
2- 11 Reaction between epoxy groups with acid group .................................................... 18
2- 12 Transition-metal-catalyzed ATRP ............................................................................ 23
2- 13 Representative acrylates polymerized by ATRP ...................................................... 24
2- 14 Schematic representation of controlled topologies, compositions, and functionalities
and molecular composites prepared by ATRP ............................................... 25
2- 15 Urethane formation via the reaction of isocyanate with polyol ............................... 26
2- 16 Aromatic isocyanate chemical structure .................................................................. 26
xiii

2- 17 Aliphatic isocyanate chemical structure .................................................................. 27
2- 18 Intramolecular hydrogen bonds formation in the NIPU .......................................... 28
2- 19 Mechanism for reaction between cyclic carbonate and amine ................................ 30
2- 20 Typical cyclic carbonate monomers structure ......................................................... 32
2- 21 Mechanism for quaternary onium salt catalyzed reaction between oxirane and CO
2

....................................................................................................................... 33
2- 22 Reaction of bis-cyclic carbonate with diamine ....................................................... 35
2- 23 Multifunctional cyclic carbonate oligomers structure ............................................. 37
2- 24 Reaction of l-lysine with biscyclic carbonate ......................................................... 38

3- 1 Chemical structure of diacids, diols and representative SPE and UPE ..................... 53
3- 2 Synthesis of polyester-poly(meth)acrylates block copolymers. ................................ 54
3- 3 (a) Kinetic plots of ATRP of MMA (lines 1 and 2) and EMA (lines 3 and 4) in
acetone at 50
0
C using UPE1 as macroinitiator. Lines 1 and 3:
CuBr/Me6TREN and lines 2 and 4: CuCl/Me6TREN catalysts. (b) Kinetic
plots of ATRP of EA (line 1), BA (line 2) and EHA (line 3) using UPE2
macroinitiator in acetone and CuBr/Me6TREN catalyst at 50
0
C ................. 57
3- 4 GPC traces of (a) UPE1, (b) PMMA-b-UPE1-b-PMMA triblock copolymer and (c)
PBA-b-PMMA-b-UPE1 b-PMMA-b-PBA pentablock copolymers,
respectively. ................................................................................................... 58
3- 5 GPC traces of starting (a) UPE2, (b) PBA-b-UPE2-b-PBA triblock copolymer and (c)
PMMA-b-PBA-b UPE2-b-PBA-b-PMMA penta-block copolymers,
respectively .................................................................................................... 59
3- 6 The NMR spectra of (a) UPE1 macroinitiator (b) PMMA-b-UPE1-b-PMMA and (c)
PEA-b-UPE2-b-PEA tri-block copolymers, respectively.............................. 61
3- 7 GPC traces of (a) SPE1, (b) PMMA-b-SPE1-b-PMMA and (c) PEMA-b-SPE1-b-
PEMA tri-block copolymers, respectively .................................................... 65
3- 8 GPC traces of (a) SPE2 macroinitiator, (b) PBA-b-SPE2-b- PBA and (c) PEHA-b-
xiv

SPE2-b-PEHA tri-block copolymers, respectively. ....................................... 65
3- 9 GPC traces of (a) PEHA-b-SPE2-b-PEHA tri-block and (b) PMMA-b-PEHA-b-
SPE2-b-PEHA-b-PMMA penta-block copolymers, respectively.................. 66
3- 10 The DSC thermograms of (a) PMMA-b-PEHA-b-UPE2-b- PEHA-b-PMMA, (b)
PMMA-b-UPE1-b-PMMA, (c) UPE, (d) PEA-b- UPE2-b-PEA, (e) PBA-b-
UPE2-b-PBA and (f) PEHA-b-UPE2-b-PEHA copoymers, respectively ..... 67
3- 11 The DSC thermograms of (a) SPE, (b) PEHA-b-SPE2-b- PEHA, (c) PMMA-b-
SPE1-b-PMMA, (d) PMMA-b-SPE1-b-PMMA and (e) PMMA-b-PEHA-b-
SPE2-b-PEHA-b-PMMA copolymers, respectively. ..................................... 68
3- 12 Heat flow versus time plot of a series of UV-curable polyesters: (a) neat UPE and
(b), (c), (d) are three different PEHA-b-UPE-b-PEHA copolymers of
molecular weights 5550, 7400 and 9600, respectively. ................................. 70

4- 1 General synthetic scheme for (a) urethane, (b) urea .................................................. 73
4- 2 General synthetic scheme for preparation of polyurea and polyurethane from the
blocked isocyanate......................................................................................... 74
4- 3 Structures of the monomers for preparation of polyester polyols ............................. 76
4- 4 Reaction strategy for preparation of coatings, (a) polyester-urethane-urea (PUU)
coatings, (b) polyester-urethane (PU) coatings ............................................. 82
4- 5 IR spectrum of partially blocked HDI isocyanurate (PBH) ...................................... 83
4- 6 NMR of partially blocked HDI isocyanurate (PBH), (a)
1
H NMR and (b)
13
C NMR
....................................................................................................................... 84
4- 7 Tensile properties of PUU and PU coatings, (a) tensile strength, (b) tensile modulus,
(c) elongation at break ................................................................................... 85
4- 8 Modulus (E) as a function of temperature of polyurethane-urea (PUU) and
polyurethane (PU) coatings based on (a) AA-BD, (b) AA-PD, (c) AA-HD, (d)
AAIPA-HD .................................................................................................... 87
4- 9 Tan as a function of temperature of polyurethane-urea (PUU) and polyurethane
(PU) coatings based on (a) AA-BD, (b) AA-PD, (c) AA-HD, (d) AAIPA-HD
....................................................................................................................... 88
4- 10 Reaction mechanism for preparation of the polyester polyurethane-urea coatings . 91

5- 1 Nonisocyanate polyurethane preparation procedure ................................................ 99
5- 2 FTIR spectra of hyrdroxyl terminated polyester (H-PE), epoxidized polyester (E-PE)
xv

and cyclic carbonate polyester (CC-PE)...................................................... 100
5- 3
1
H NMR spectra (300 MHz, CDCl
3
) of hyrdroxyl terminated polyester (H-PE),
epoxidized polyester (E-PE) and cyclic carbonate polyester (CC-PE) ....... 100
5- 4
13
C NMR spectra (300 MHz, CDCl
3
) of hyrdroxyl terminated polyester (H-PE),
epoxidized polyester (E-PE) and cyclic carbonate polyester (CC-PE) ....... 101
5- 5 FTIR spectra of CC-PE formation with time........................................................... 102
5- 6 FTIR spectra of non-isocyanate polyurethane formation with time by using CC-PE
cured with IPDA under 70
o
C (NH
2
/CC=1.25) ............................................ 103
5- 7 FTIR spectra of non-isocyanate polyurethane formation at different amine to cyclic
carbonate ratio by using CC-PE cured with IPDA under 70
o
C ................... 103

6- 1 Photoinitiators chemicals structure ...........................................................................115
6- 2 UDMA reactive diluents synthesis scheme ..............................................................116
6- 3 NMR of EOAEC urethane diol, (a) 1H NMR and (b) 13C NMR ............................118
6- 4 NMR of POAEC urethane diol, (a)
1
H NMR and (b)
13
C NMR ..............................118
6- 5 NMR of POAPC urethane diol, (a)
1
H NMR and (b)
13
C NMR ..............................119
6- 6 NMR of EOAED urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR ........... 120
6- 7 NMR of POAED urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR ........... 120
6- 8 NMR of POAPD urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR ........... 120
6- 9 The synthesis of oligomer acrylated polyester (APE) ............................................. 122
6- 10
1
H NMR of (a) polyester polyol and (b) acrylated polyester ............................... 123
6- 11 The viscosity of the synthesized urethane diols and corresponding urethane
dimethacrylates ............................................................................................ 124
6- 12 Viscosity behavior of neat APE oligomer and APE/reactive diluent mixtures ...... 125
6- 13 Polymerization conversion (a) and polymerization rate (b) of EOAED reactive
diluents as a function of exposure time for different type PI with 2 wt %
concentration ............................................................................................... 128
6- 14 Polymerization conversion (a) and polymerization rate (b) of EOAED reactive
diluent as a function of exposure time for PI Darocur 4265 with different
xvi

concentration ............................................................................................... 129
6- 15 Polymerization conversion (a) and polymerization rate (b) of APE oligomer and
four reactive diluents as a function of exposure time at 2.0 wt % PI Darocur
4265 concentration ...................................................................................... 130
6- 16Polymerization conversion as a function of exposure time of the formulation of APE
with different reactive diluents: (a) EGDMA, (b) EOAED, (c) POAED, and
(d) POAPD .................................................................................................. 132
6- 17 Polymerization rate as a function of exposure time of the formulation of APE with
reactive diluents: (a) EGDMA, (b) EOAED, (c) POAED, and (d) POAPD 133

7- 1 The aryl ketone chemical structure .......................................................................... 137
7- 2 Reactive diluents chemical structure ....................................................................... 144
7- 3 Tensile properties of UV cured coating as a function of reactive diluents: (a) tensile
strength; (b) elongation at break; (c) tensile modulus ................................. 149
7- 4 Dynamic mechanical properties of EOAED coating system. E storage ................ 151
7- 5 Modulus (E) as a function of temperature of the UV curable coating with different
reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d) POAPD
..................................................................................................................... 153
7- 6 Tan as a function of temperature of the UV curable coating with different reactive
diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d) POAPD ......... 154
7- 7 DSC thermograms as a function of temperature of the UV curable coating with
different reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d)
POAPD ........................................................................................................ 155
7- 8 TGA thermograms as a function of temperature of the UV curable coating with
different reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d)
POAPD ........................................................................................................ 157
7- 9 Effect of the reactive diluent type and content on the gel content properties of UV
cured coatings .............................................................................................. 160
7- 10 Effect of the reactive diluent type and content on the water absorption properties of
UV cured coatings ....................................................................................... 161


xvii

LIST OF TABLES

Table Page
3- 1 Properties of hydroxyl-telechelic polyesters ............................................................. 52
3- 2 Results of ATRP of different (meth)acrylates using UPE-based macroinitiators ...... 56
3- 3 Results of ATRP of MMA and EMA using SPE-based macroinitiators .................... 63

4- 1 Physical property of the synthesized polyester polyols ............................................. 79
4- 2 Formulation of polyurethane-urea (PUU) and polyurethane (PU) coatings.............. 81
4- 3 Tensile properties of of polyurethane-urea (PUU) and polyurethane (PU) coatings . 86
4- 4 Viscoelastic properties of polyurethane-urea (PUU) and polyurethane (PU) coatings
......................................................................................................................... 89
4- 5 Coating properties of polyurethane-urea (PUU) and polyurethane (PU) coatings .... 90

6- 1 Photopolymerization kinetics data as a function of photoinitiator type (with 2 wt %)
and photoinitiator Darocur 4265 concentration ............................................ 129
6- 2 Photopolymerization kinetics data as a function of reactive diluent type and
concentration ................................................................................................. 130

7- 1 The formulation of non-isocyanate PU with different reactive diluents at different
concentration ................................................................................................. 145
7- 2 Tensile properties of UV cured coating as a function of reactive diluents type and
content ........................................................................................................... 150
7- 3 Viscoelastic properties of UV cured coating as a function of reactive diluents type
and content .................................................................................................... 152
xviii

7- 4 DSC data of UV cured coating as a function of reactive diluents type and content 156
7- 5 Thermogravimetric Analysis (TGA) data of UV cured coating as a function of
reactive diluents type and content ................................................................. 158
7- 6 General coating properties as a function of reactive diluents type and content ...... 162

1

CHAPTER I

INTRODUCTION

Polyesters are widely used in coating applications, and generally synthesized by
polycondensation reaction of various diacids and diols. Most of the polyesters used in the
coating industry have low molecular weight (oligomer), and are amorphous, branched.
The polyesters are usually crosslinked with isocyanates, melamine or epoxy groups via
the thermal curing process and used for coating applications.
Polyesters based organic coatings have appreciable mechanical properties such as
high tensile strength together with flexibility. But the presence of ester linkages in the
backbone of polyesters makes them vulnerable to hydrolysis. On the other hand,
poly(meth)acrylates are better abrasion resistant, hydrolytically stable with superior
mechanical properties. Hence, to improve the hydrolytic/oxidative stability and to
achieve chemical abrasion resistance properties, it is highly desirable to prepare
polyesters and poly(meth)acrylates hybrid organic coating. But there is no report of the
synthesis of block copolymers of polyesters with (meth)acrylates in which polyesters are
synthesized by reacting small-molecular-weight diacids and diols. Thus, the first focus
(Chapter III) of this work was to synthesize different block copolymers of Unsaturated
and Saturated Polyesters (UPE and SPE, respectively) with (meth)acrylates. This block
copolymer has well-defined molecular weight and narrow polydispersity by combination
2

of condensation polymerization and ATRP. This work also shows that the unsaturation
present in the main chain of the polyesters is almost unaffected during ATRP. The
synthesized unsaturated polyester/(meth)acrylate block copolymers can form crosslinked
networks upon irradiation. These copolymers might be interesting candidates for coatings
with better overall properties than those based on neat polyesters.
Polyester based polyurethane coatings have wide applications in wood,
automotive, industrial, and coil coatings due to their high elasticity, toughness, and
abrasive properties. Typically, polyurethanes are obtained by the reactions of
polyisocyanates with polyols.
Compared with polyurethane coating, polyurea coating has less wide applications
due to two major drawbacks. One is the faster curing of the polyurea, the reaction of the
isocyanate and amine could be cured within seconds, which makes it good for only two-
component spray coating application but limits its wide application for other coatings.
Another drawback is that polyamine starting raw material for polyurea is very limited,
and usually polyamine is based on the polyether amine. Thus, the second focus (Chapter
IV) of this work was to prepare polyester polyol based Polyurethane-Urea (PUU)
coatings. These PUU coatings were prepared by formulating polyester polyol, partially
blocked isocyanate and isophorone diamine. Such PUU coatings were expected to have a
longer pot life than conventional 2K polyurea or polyurethane coating due to the use of
partially blocked isocyanate, a better mechanical property than polyurethane coating due
to the existence of the extra urea function group, and a better abrasion resistance and
chemical resistance property than polyether polyurea coating due to the existence of the
ester function group.
3

One drawback of these polyester polyurethane coatings is their toxic property.
The isocyanates starting materials for preparation of polyurethanes are toxic. Exposure to
isocyanate can result in health effects such as skin irritation. Also, phosgene is a more
toxic material, which is used for preparation of the isocyanate. Alternately, it was known
that the carbamate group can be synthesized by the reaction of the primary amine with
cyclic carbonate. This provides a useful way to obtain polyurethanes via a non-isocyanate
method. Thus, the third focus of this work was to synthesize polyester based non-
isocyanate polyurethane (NIPU) coatings by either thermal curing (Chapter V) or UV-
curing (Chapter VI and VII).
Thermal curable NIPU are usually prepared from the reaction of polyamine and
poly(cyclic carbonate). The poly(cyclic carbonate)s are usually prepared by the reaction
of poly(epoxide)s under CO
2
in the presence of catalyst. Most of poly(epoxide)s for
nonisocyanate polyurethane synthesis reported are low molecule monomers or polyether
based oligomers. It is well known that polyester is a widely used polyol reagent to
prepare polyurethanes. But, there is no report of the synthesis of nonisocyanate
polyurethanes by using epoxidized polyester oligomer as starting material. Thus, chapter
V was focused on synthesis of cyclic carbonate terminated polyester and thus preparation
of NIPU.
UV-curable coatings offer many advantages, such as rapid curing, high-energy
efficiency and low Volatile Organic Compound (VOC). Photopolymerization can occur
at relatively low temperature with a nature of ultrafast curing, which makes UV-curable
coating suitable for a widely application in the market sectors where temperature
sensitive substrates are coated, like wood, paper and plastics. Most UV-curable coating
4

systems are free radical based on acrylated oligomers formulated with (meth) acrylate
reactive diluents.
UV-curable polyester polyurethane coatings are usually prepared by formulating
of the urethane acrylate oligomer with (meth)acrylate reactive diluents. Urethane acrylate
is usually prepared by the reaction of a polyester polyol with a diisocyanate to yield an
isocyanate terminated oligomer. These oligomers are then reacted with a hydroxyethyl
acrylate monomer. UV-curable NIPU coating has never been reported, even though Non-
isocyanate Urethane Dimethacrylate (NUDMA) monomers have been prepared, and their
photopolymerization properties have been studied by photoinitiated differential scanning
calorimetry. Thus, in this work, UV-curable NIPU polyurethane coatings were prepared
by formulating of Acrylated Polyester (APE) oligomer with NUDMA. Chapter VI was
focused on the investigation of photopolymerization kinetics of NUDMA and their
formulations with APE by using real time Fourier transform infrared spectroscopy
(FTIR). Chapter VII was focused on the investigation of the viscoelastic, tensile, thermal,
and general coating properties.

5

CHAPTER II

BACKGROUND

2.1 Polyesters
Polyesters are polymers which contain the ester repeat units. Polyesters can be
obtained by a wide range of reactions, and one of the important reactions is the
polyesterification between dibasic acids and diols.
2.1.1 Polyesters history
The first polyesters were synthesized through the reaction of tartaric acid and
glycerol by Berzelius in 1847
1
. In 1901, glyptal polyesters were first produced by
heating glycerol and phthalic anhydride. At first heating, linear polyester was formed
through reaction of the two primary hydroxyl groups in glycerol, and by further heating;
cross-linked polyesters were formed through reaction of the third alcohol. The first
commercially available polyesters Glyptals

were made by GE in the 1920s. Glyptals
were initially developed for coating application and are now commonly known as alkyd
resins. Glyptals were produced by the reactions of glycerol, phthalic anhydride, and the
fatty acids of various oils. The double bonds in the fatty acids of the oils can be further
6

oxidized, giving a cross-linked product
2
. Later on, other polyols such as Monoethylene
Glycol (MEG), propylene glycol, pentaerythritol and acids such as
maleic anhydride, Isophthalic Acid (IPA), Terephthalic Acid (TPA) were used to vary the
properties of the alkyd resin.
In the late 1920s, W. H. Carothers and his collaborators began to make polyesters
with the molecular weight between 2500 and 5000 from the reaction of aliphatic diacids
with diols
3
. The modern history of polyesters began in 1930s when he established the
relationship between polymerization, conversion, functionality and gel point
4
.
However, Carothers's polyesters had a low melting point and poor hydrolytic
stability. In the early 1940s, Whinfield and Dickson synthesized polyesters by using
apliphatic diols and aromatic acids, instead of alphatic acids
5
. Among these high-
melting-point polyesters, Poly (Ethylene Terephthalate) (PET) and Poly (Butylenes
Terephthalate) (PBT) are the most economically important types.
In the late 1930s, a new type of thermosetting resin based on unsaturated
polyester was prepared by the polycondensation reactions involving mixtures of saturated
and unsaturated dibasic acids or anhydrides with aliphatic diols
6
. By dissolving this kind
of unsaturated polyester in styrene, the thermosetting resin was formed. Now, the
unsaturated polyesters have been widely used as important matrix resins for glass fiber
reinforced composites.
In the late of 1950s and 1960s, with the development of the polyurethane
chemistry and technology, the aliphatic polyesters were first found their commercial
applications. Much attention was focused on block copolymer in 1970s, and high-
performance wholly aromatic polyesters in 1980s
2
. In the 1990s, much intensive research
7

was carried on the recyclable and/or biodegradable polyesters such as poly (lactic acid)
(PLA), poly (-caprolactone) (PCL), poly (hydroxyalkanoates) (PHAs) because of the
increasing environmental concerns
7
. During this time, a new type of polyester
hyperbranched polyaryl esters appeared
8
. Hyperbranched polymers belong to the class of
dendritic polymers which provide lower viscosity, better solubility, lower crystallinity,
and a larger number of end function groups
9
. Up to now, various polyesters including
aliphatic polyesters, aromatic-aliphatic polyesters, wholly aromatic polyester have been
prepared. And these polyester materials have been widely used as fibers, engineering
plastics, high-performance polymers, thermosetting resins, elastomers as well as coatings.
This dissertation deals with the polyester in coating fields only.
2.1.2 Synthetic methods
Generally speaking, there are three ways to prepare polyesters: equilibrium
polyesterifications, nonequilibrium polyesterifications, and nonpolyesterifications.
Equilibrium polyesterifications are equilibrium process because the equilibrium constant
is generally low (K 4 for carboxylic acid-alcohol reactions)
2
; these polyesterifications
are usually carried out at high temperature through bulk polymerization via hydroxyl-
carboxyl reactions, hydroxyl-ester, and carboxyl-ester interchange reactions.
Nonequilibrium polyesterifications usually have high equilibrium constant (K = 4700 for
acid chloride-phenol polyarylate synthesis)
10
; these polyesterifications are usually
carried out at low temperature through solution polymerization by using highly reactive
monomers such as acid chlorides. Nonpolyesterifications usually include epoxy-carboxyl
reactions
11, 12
, ring-opening polymerization of cyclic esters
7
, and some miscellaneous
reactions
13
.
8

2.1.2.1 Equilibrium polyesterifications
These reactions are usually carried out at high temperature (>180
o
C) via bulk
polymerization in the presence of external catalysts which can be strong protic acids,
metal oxides, metal salts, and organometallic compounds of titanium, tin, zirconium
14
.
Among these catalysts, metal catalysts especially titanium alkoxides and tin compounds
are preferred industrially because strong protic acids tend to catalyze side-reactions
15,16
.
The small molecule formed during the reaction is usually removed to drive the reaction to
completion by adding the toluene or xylene (5-15% mass) into the reaction medium by
formation of the azeotropic mixture, and eliminated by applying the vacuum in the last
step of the reaction
17
.
Direct polymerizations: These are the most widely used method for the synthesis
of polyesters, which can be got by the reactions of diacids and diols, acid anhydrids and
diols, or hydroxyl acids, as shown on Figure 2- 1.

9


Figure 2- 1 Polyester synthesis by direction polymerization
Transesterification polymerizations: These include hydroxyl-ester
18
, carboxyl-
ester
19
, and ester-ester reactions. Among of these, the hydroxyl-ester reaction is the most
important one; it is usually used for synthesis of aromatic-aliphatic and wholly aromatic
polyesters, such as the PET and PBT polyester synthesis. Carboxyl-ester reaction is
limited to synthesis of wholly aromatic polyesters, while ester-ester reaction is rarely
used because the reaction is very slow
2
.
2.1.2.2 Nonequilibrium polyesterifications
The nonequlibrium polyesterifications are irreversible reactions having the high
equilibrium constant. These reactions usually involve acid chlorides or activated

HOOC R COOH
+
HO R' OH
160-290
o
C.
Bulk/Cat.
HO
R'
O R O
H
O O
n
HO R COOH
160-290
o
C.
Bulk/Cat.
R O
H HO
O
n
R
O
C
O
C
O
+
HO R' OH
100-150
o
C.
Bulk/Cat.
HO
R'
O R O
H
O O
160-290
o
C.
Bulk/Cat.
HO
R'
O R O
H
O O
n
a: Reactions of Diacids and Diols
b: Reactions of Hydroxyl Acids
c: Reactions Acid Anhydrids and Diols
10

carboxylic acids with diols in solution. The nonequlibrium polyesterifications can yield
high molecular weight polymers in the mild conditions in a short time without side
reactions. So they are suited for synthesis aromatic polyesters having high melting point
20
, polyesters bearing function groups which are unstable at high temperature
21
. They are
also useful for synthesis cyclic oligomers
22
.
Acid Chloride-Alcohol Reactions. Figure 2- 2 shows a typical acid chloride-
alcohol reaction which was carried out in THF or CH
2
Cl
2
in the presence of the tertiary
amines at -10 to 30
o
C
23
.

Figure 2- 2 Ester synthesis via acid chloride and alcohol reactions
Activation Polyesterification: These reactions were carried out by using
dicarboxylic acids and diols as reactants in mild conditions in the presence of the
activating agents which can transform the dicarboxylic acid into a more reactive
intermediate. Trifluoroacetic anhydride, 1,1-carbonyldiimidazole
24
, carbodiimides
25
,
tosyl
26
and picryl
27
chlorides, and phosphorus derivatives
28
have been used as the
activating agents. As shown in Figure 2- 3, when N, N-dicyclohexylcarbodiimide (DCC)
was used as activating agent, condensation occurs between equimolar acids and alcohols,
and produced water will react with carbodiimide groups to form the stable urea byproduct
25
. By using DCC as activating agent, low-molar-mass (Mn=5000-9000) aliphatic
polyesters
29
, aromatic polyesters starting from hydroxyacids
30
, and poly(benzyl ester)
dendrimers
31
were synthesized.


+ HO-R' R-COCl
CH
2
Cl
2
, Et
3
N
-10 to 30
o
C
RCO-OR'
+
Et
3
NH
+
Cl
-
11


Figure 2- 3 Ester synthesis via acid and alcohol reaction by using N, N-
dicyclohexylcarbodiimide (DCC) as activating agent
2.1.2.3 Nonpolyesterifications
Epoxy-Carboxyl Reaction: At lower temperature (100-120
o
C), this reaction takes
places between the epoxides and carboxylic acids forming polyesters bearing pendant
secondary hydroxyl groups
32, 33
as shown in Figure 2- 4. At higher temperature, side
reactions happen, such as esterification of secondary hydroxyl groups or the ring-opening
polymerization of epoxy groups. By using this kind of reaction, polyester powder
coatings can be prepared
34
.


Figure 2- 4 Ester synthesis via epoxy-carboxyl reaction
Cyclic Easters Ring-Opening Polymerization (ROP): ROP of cyclic esters and
related compounds is an alternative method for the synthesis of aliphatic polyesters,
especially degradable aliphatic polyesters such as poly (lactic acid) (PLA), poly (glycolic
acid) (PGA), and poly (-caprolactone) (PCL). Figure 2- 5 shows PCL synthesis via the
ROP of -caprolactone cyclic ester. Review is available on the cyclic esters ring-opening
polymerization to prepare biodegradable aliphatic polyester
35
.


N C N
+
RCOOH R'OH +
RCO-OR' +
H
N C
H
N
O

RCOOH
+
O
OR'
100-120
o
C
R O OR'
O
OH
12


Figure 2-5 Poly (-caprolactone) (PCL) synthesis via ring-opening polymerization
(ROP)
2.1.3 Raw materials
Most of polyesters in coatings fields have relatively low MWs and are amorphous
and branched, and they must be cross-linked in order to form useful coating films. Figure
2- 6 shows the most important polyols (diols and triols) and Figure 2- 7 shows the most
important polyacids used as raw materials for synthesis of polyesters
34
.


Figure 2-6 The important polyols used for polyesters synthesis


O
O
1-dodecanol
Sn(Oct)
2
160C
O CH
2
5
C
O
n
HO OH
HO
OH
HO OH
HO
HO OH
HO
OH
Neopentyl glycol (NPG)
Cyclohexanedimethanol (CHDM)
Hexane diol (HD)
Trimetheylolpropane (TMP) Pentaerythritol (PE)
OH HO
13


Figure 2-7 The important polyacids used for polyesters synthesis
All of the polyols used for polyester synthesis are aliphatic ones. NPG is the most
widely used hindered diol, HD is the most widely used linear diol, and TMP is the most
widely used triol.
NPG has excellent exterior durability because there is no labile hydrogen with
respect to the hydroxyl functionality. The two methyl groups increase the steric hindrance
that imparts chemical resistance, stability towards hydrolysis and corrosion resistance. Its
two primary hydroxyl functions ensure good reactivity not only during condensation but
also during subsequent crosslinking.
CHDM esterifies more rapidly than NPG, and CHDM based polyesters give cured
films with MF resins rapidly than NPG based polyesters
36
, since the two primary
hydroxyl groups are less hindered than NPG. The cycloaliphatic structure represents an
excellent compromise between hardness and flexibility, which leads to thermal stability
and low coloration during curing
37
.

O
O
O
COOH
COOH
O
O
O
HOOC
COOH HOOC
COOH
COOH
COOH
5
7
7
4
Phthalic anhydride (PA) Isophthalic acid (IPA) Hexahydrophthalic anhydride
(HHPA)
Adipic acid (AA) Azelaic acid (AzA)
Dimer fatty acid
14

TMP and PE are used to make branched polyesters and increase the functionality
of the polyester polyols. PE is little used in polyester resins since this gives resins with
too much functionality and very high viscosities.
The polyacids used for polyester synthesis can be aliphatic or aromatic, linear or
hindered. Isophthalic acid (IPA) is the most widely used aromatic acid and adipic acid
(AA) the most widely used aliphatic acid. Aromatic polyacids are mostly used to increase
the hardness of the polyesters. Phthalic anhydride (PA), isophthalic acid (IPA) and
terephthalic acid (TPA) are three important aromatic diacids.
Phthalic anhydride (PA) in polyesters has a rather limitation in coatings
applications due to its rather poor exterior resistance. PA based polyester coatings are
considered to be used for base coating and not recommended for exterior or high
performance coatings. Phthalic anhydride is frequently used for preparation of alkyd
resins, where cost and not performance is the overriding factor
38
.
Isophthalic acid (IPA) enables the mechanical properties, chemical resistance and
hardness to be significantly improved compared to those obtained by using PA. IPA is
less reactive than PA and it gives resins that are slightly less soluble. However, IPA
remains one of the key products for polyester resins for surface coatings. With its higher
melting point, it leads to longer reaction times and is slightly more difficult to use.
Terephthalic acid (TPA) further increases the heat resistance and mechanical
properties of polyesters compared to either PA or IPA, but it also reduces the solubility of
resins containing it and has a strong tendency towards crystallisation. TPA is less reactive
than IPA and requires higher reaction temperatures and the use of catalysts.


15

Cyclohexane dicarboxylic acid (CHDA) represents an excellent compromise
between hardness and flexibility. Corrosion resistance is better than with linear polyacids.
Exterior resistance is also better than that from aromatic compounds or aliphatic/aromatic
mixtures used for establishing the best compromise between hardness and flexibility. It
has good solubility in most of the liquid diols used and its reactivity is quite good. It has
poor dilution characteristics in solvents. Its thermal resistance is good and the ranges of
colors of the resins obtained are good due mainly to its symmetrical structure.
Trimellitic anhydride (TMA) can be used to increase the functionality of the
polyesters without significantly increase the viscosity and the molecular weight. It also
can be used to prepare water dispersible polyester.
Hexahydrophthalic anhydrite (HHPA) is used when a very high resistance at
hydrolysis and excellent yellowing and external resistance are required. However its
expensive and only used where its benefits justify the extra cost, such as water dilutable
products, which require excellent hydrolytic stability, or for automobile coatings which
need good color and light stability, such as white topcoats.
Adipic acid (AA) is one of the most frequently used linear diacids since it gives
an excellent compromise in terms of technical performance and price. Diacids with much
longer chains are significantly more expensive, thus they are limited to specific
applications
2.1.4 Hydrolytic stability
The polyesters properties such as thermal properties, solubility, density,
hydrolytic stability, and crystallinity are related with the polyester structure parameters
such as the nature-aliphatic or aromatic in the polyester chains, ester group content, the
16

presence, nature and position of substitution on the monomer units, and the number and
nature of comonomers. Among of polyester properties for coatings, the hydrolytic
stability is the most important ones.
The ester linkage is susceptible to hydrolytic cleavage giving back carboxyl and
hydroxy end groups. Most polyester undergoes degradation when heated in the presence
of water. The degradation reaction is accelerated in the presence of acid or base catalysts
(Figure 2- 8). The structural parameters that govern the hydrolytic degradation of
aliphatic polyesters have been examined by several authors for the design of
biodegradable materials
39, 40
. The hydrolysis susceptibility of polyester depends on the
concentration of ester bonds, on the polyester polyol acidity, on the hydrophobicity of the
glycol or dicarboxylic acid used for polyester synthesis, and on the steric hindrance
around the ester groups. As a rule, polyesters from sterically hindered diols, diacids, or
hydroxy acids and polyesters with aromatic units offer superior hydrolytic resistance. 2,2-
Dimethyl-1,3-propanediol, hydrogenated bisphenol-A, , -disubstituted hydroxyacids,
and aromatic monomers are often used for this purpose. On the other hand,
hydrolyzable/biodegradable polyesters are unhindered polymers: aliphaticaromatic
copolyesters or polyesters from - or -hydroxyacids, or from nonsubstituted aliphatic
lactones
2
.

Figure 2- 8 Ester group hydrolysis
The intensive research done in the last few years proved that the hydrophobicity
of the glycol or of the dicarboxylic acid used for polyester polyol synthesis is one of the

R
C
O
R'
O
H
2
O
R
C
HO
R'
O
OH
17

most important parameters to improve the hydrolysis resistance of polyester. Thus, the
relative order of hydrolysis resistance of some usual polyester is exactly the order of
hydrophobicity
41
:
AA-HD > polycaprolactone > AA-BD > AA-DEG
Some new developed glycols, which had hydrophobic groups and relatively high
steric hindrances, were used to improve the hydrolysis resistance of polyeste (BEPG;
Kyowa Hakko Kogyo Co. Ltd.), (see Figure 2- 9).

Figure 2-9 Diols with hydrophobic groups used in hydrolysis resistant polyester
polyol synthesis
41

2.1.5 Polyesters crosslinking mechanism
The formation of a paint film based on a polyester resin implies that it must be
crosslinked or hardened with an external crosslinking agent. Indeed, polyester resins do
not have sufficient film-forming properties except for thermoplastic polyesters. The
polyester can be crosslinked either through acid functionality or hydroxyl functionality.
2.1.5.1 Crosslinking through carboxylic groups
(a) With Melamine Formaldehyde (MF) resins. A melamine formaldehyde resin is
a member of the aminoplast family, which encompasses urea formaldehyde and
benzoguanamine formaldehyde resins that act as crosslinking agent. At a temperature
above 120C, the following reaction is observed (Figure 2- 10)
38
.

HO
OH HO OH
18


Figure 2- 10 Reaction between MF resins with acids
This reaction continues until a hard, completely crosslinked film is obtained. The
ratios of polyesters and aminoplast resin vary within the range 60/40 to 80/20 depending
upon temperature, nature of melamine resin and the final characteristics of the paint
required. Resins of the hexamethoxymelamine type are used for temperatures starting
from 150C, and methylated, butylated or isobutylated formaldehyde resins can also be
used. It should be noted that normally this reaction is not designed into polyesters, with
the more traditional hydroxyl aminoplast reactions predominating.
(b) With an epoxide resins. This reaction is extensively used in powder coatings,
more particularly in hybrid systems that are carboxyl functional polyester systems with
epoxy resins, in ratios varying between 50/50 to 70/30. The following reaction takes
place (Figure 2- 11)

Figure 2- 11 Reaction between epoxy groups with acid group
2.1.5.2 Crosslinking through the hydroxyl functions
(a) With an MF resins. The hydroxyl functionality in a polyester resin can react
with the ether linkages of the melamine resins through transetherification reactions that

R N
O
O
HOOC COOH
R N
O
O
O
COOH

O
O
O
OH
OH
O
19

lead to the formation of volatile alcohols. This reaction is principally used in
thermosetting liquid paints and is catalysed by acids such as para-toluene-sulphonic acid.
In water-dilutable polyesters there is a potential problem of interaction between
neutralising amines and the acid used for catalysis. The neutralising agent may generate
significant surface defects. For this reason special blocked catalysts have been developed
42
. The curing temperatures range from 120C to 160C for polyester/melamine ratios
varying between 60/40 to 90/10. These can be found in the majority of thermosetting
liquid systems, particularly when their very good compromise between performance and
cost price is considered
43
.
(b) With a blocked polyisocyanate. This system is particularly used in coil coating
and automobile applications. It enables the hydroxyl functionality of polyester to be
crosslinked with polyisocyanate using a single pack system. Crosslinking will only occur
with a blocked polyisocyanate or with a mixed crosslinking system, such as melamine
with a blocked polyisocyanate. The presence of urethane links enables the mechanical
properties and exterior resistance to be improved when required. In liquid coatings, the
polyesters used have hydroxyl values of about 110 to 180 mg KOH/g, whereas in powder
coatings, polyesters have much lower hydroxyl content (ca. 40 to 110 mg KOH/g). The
ratio of powder polyester / polyisocyanate varies from 60/40 to 80/20 for temperatures of
20 minutes at 170C to 10 minutes at 200C. The blocked polyisocyanate are either
blocked polyisocyanate, for example with caprolactam, which leads to the release during
curing of this blocking agent; or uretidiones, which are in fact diisocyanate dimers (such
as the dimer of IPDI), which in these cases does not lead to the release of volatile
compounds
44,45,46
.
20

2.2 Hybrid polyesters
Hybrid materials usually contain at least two components. They can be organic-
inorganic hybrids or organic hybrids. Hybrid polyesters are usually prepared to improve
the hydrolytic stability and mechanical propreties of the neat polyesters.
2.2.1 Organic-Inorganic hybrid materials
Also named ceramers, represent the natural interface between organic chemistry
and inorganic chemistry. This fairly new class of materials, whose first examples date
back to the eighties
47
, may take advantage from characteristic properties of both organics
and inorganics, such as high ductility and low temperature processing conditions typical
of polymers and high modulus, thermal stability and low coefficient of thermal expansion
distinctive of inorganic materials
48
. Moreover, organicinorganic hybrids may display
synergistic properties with respect to the bare sum of the plain components features,
such as remarkable improvements in mechanical, thermal, electrical, and magnetic
properties. In particular, the nano-structured morphology of the inorganic domains
strongly affects the physical behavior of the hybrids leading to interesting properties such
as optical transparency
49
. Due to the wide range of applicability fields of this class of
materials, a number of hybrids are already commercially available
50
. A wide spectrum of
polymers are employed as the organic phase constituent of creamers:
Polydimethylsiloxane (PDMS)
47,51
, poly(tetramethylene oxide) (PTMO)
52
,
polycaprolactone (PCL)
53, 54
, polyoxazoline
55
, poly(ether ketone)
56
, polyethylene oxide
57
, etc. The hybrid inorganic phase is usually a metal oxide. Although many oxides are
reported in the literature, such as those of titanium, zirconium, aluminium or cerium,
21

silicon oxide (silica) is the most widely applied in ceramers
58
, owing to the easiness of
its preparation.
2.2.2 Organic hybrid materials
Another class of hybrid polymers is composed of at least two kinds of organic
polymers, normally incompatible, and again covalently bonded to each other. The main
in
59
terest of these materials is to intimately combine the properties of the different kinds
of polymers.
Siliconised Polyester Hybrids. Modification with organosilicone is one of the
ideal methods available for improving the hydrophobicity and heat resistance of polyester.
Poly(dimethylsiloxane)s (PDMS) is the most widely used organosilicone. Siliconised
polyesters can be used in cookware applications. Coil coated architectural claddings is
another major application of siliconised polyesters. In this application, the siliconisation
imparts good external durability while choosing suitable polyesters with super exterior
durability. The polyesters are usually prepared from the reaction of isophthalic or
terephthalic diacids with polyols
38
. The silicone/polyester hybrid was successfully
prepared by substituting part of diol with low molecular weight hydroxyl-terminated
poly(dimethylsiloxane) (PDMS) during the esterification reaction
60
.
Poly(acrylate- ester) Hybrids. Tsavalas et al.
59
carried out with a three
component acrylic system of MMA, BA, and acrylic acid (AA) in the presence of a
Bayerr Roskydal TPLS2190 unsaturated polyester resin. Latexes were obtained in which
the polyester resin was grafted to the acrylic polymer, forming a water-based
crosslinkable coating. Both emulsions and latexes were shelf stable for over 6 months,
shear stable, and resistant to at least one freeze/thaw cycle. Resin to monomer ratios were
22

studied as high as 1:1 (wt:wt) and total emulsion solids as high as 45%. Monomer droplet
and latex particle sizes were similar, suggesting predominant droplet nucleation. A high
level of crosslinking during polymerization was observed in this particular hybrid system.
Films, both homogeneous and hard, were achieved with exceptional adhesion. Electron
microscopy showed the hybrid particle morphology has internal domains of polyester
resin in an acrylic matrix. Kinetic studies showed that as resin content increased in
comparison with monomer content, the polymerization rate decreased, suggesting
retardive chain transfer as found with the alkyds.
Epoxy-Polyester Hybrids. Bisphenol A (BPA) epoxy is a typical epoxy which is
used for preparation of epoxy-polyester hybrids. Epoxy-polyester hybrid is usually
prepared from reaction of BPA epoxy and carboxylic acidterminated polyester resins
with Mn of a few thousand. Such formulations can be used to prepare hybrid powder
coatings. Compared with epoxy powder coatings, epoxy-polyester hybrid coatings have
better color retention and UV, but still do not have good exterior durability. The epoxy-
polyester hybrid coating has wide applications including water heaters, fire extinguishers,
radiators, and transformer covers
34
.
A variety of polyesters have been used to prepare epoxy-polyester hybrid coatings.
Most are derived from neopentyl glycol (NPG) and terephthalic acid (TPA) with smaller
amounts of other monomers to adjust the Tg to the desired level and give branching to
increase the functionality above 2. An example is a polyester from NPG (364 parts by
weight, 3.5 mol), TPA (423 parts, 2.55 mol), adipic acid (AA) (41 parts, 0.24 mol), and
trimellitic anhydride (TMA) (141 parts, 0.74 mol)
61
. The acid number of the resin is 80
23

mg KOH per gram of resin. The relatively high trimellitic anhydride content increases
functionality, compensating for the low (about 1.9) functionality of the BPA epoxy.
2.3 Atom Transfer Radical Polymerization (ATRP)
Atom Transfer Radical Polymerization (ATRP) is one kind of controlled living
polymerization. It has been used to prepare polymers with well difined composition and
functionalities
62, 63, 64
. Convetional living polymerizations include cationic, anionic, and
ring-opening polymerizon. Compared to the conventional living polymerization,
controlled/living radical polymerizations (CRP) is more tolerant of functional groups and
impurities
65
. The three most well-known CRP techniques are nitroxide-mediated radical
polymerization (NMP)
66
, atom transfer radical polymerization (ATRP)
67
and reversible
addition-fragmentation chain transfer (RAFT)
68
. Figure 2- 12 shows the general
mechanism for ATRP
69
. A successful ATRP has very few termination reactions, and has
constant radical concentration. The polymer chains grow uniformly.


Figure 2- 12 Transition-metal-catalyzed ATRP
Various monomers have been successfully polymerized using ATRP: styrenes,
(meth)acrylates, (meth)acrylamides, dienes, acrylonitrile, etc. Ring-opening
polymerization is also possible. ATRP can be used to polymerize a wide range of
acrylates with various side chains (Figure 2- 13).

R-X M
t
n
-Y / Ligand
K
act
K
deact
R
K
p
X-M
t
n+1
-Y / Ligand
K
t
Termination
Monomer
24


Figure 2- 13 Representative acrylates polymerized by ATRP
ATRP of 2-hydroxyethyl acrylate (HEA)
70
and glycidyl acrylate
71
afforded well-
defined functional polymers. ATRP of poly(tert-butyl acrylate) afforded polymer with a
well-controlled fashion
72
. ATRP of monomers with long alkyd
73
and fluorocarbon
74

side chains afforded well-defined homopolymer and block copolymers. ATRP of allyl
acrylate affored polymers with cross-linking networks even at 0 C
75
. The synthesis of
various polymeric materials with novel functionalities, compositions, and architectures
are schematically represented in Figure 2- 14
69
.
O
O
O
O
O
OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
n-Butyl Acrylate (BA)
t-Butyl Acrylate (tBA)
2-Hyroxyethyl Acrylate (HEA)
Glycidyl Acrylate (GA)
Allyl Acrylate
Vinyl Acrylate (VA)
1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acrylate
7-oxooxepan-4-yl acrylate
25


Figure 2- 14 Schematic representation of controlled topologies, compositions, and
functionalities and molecular composites prepared by ATRP
2.4 Polyurethane (PU) coatings
Polyurethanes (PUs) are a class of polymers containing urethane (-NH-CO-O-)
linkage. The PUs were first discovered in 1937
76
. They are usually prepared from the
reaction of polyol and polyisocyanate. Polyurethane coatings have been widely used for
wood, plastic, automotive, industrial, and coil coatings, especially for topcoats.
Polyurethane coating have overall good mechanical properties including weathering,
flexibility, chemical resistance, abrasion resistance
77
. Two-package (2-k) coatings are the
largest volume of urethane coatings.
X X(Y) (X)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X X
X
X
X
X X
X
X
X
X
X
X
Homopolymers
Block Copolymers Statistical
Copolymers
Gradient
Copolymers
Graft Copolymers
Linear
Star / Multi- Armed Comb Copolymers Networks (Hyper) Branched
Homo/Hetero
Telechelic
Macromonomers
Star / Multi- Armed
Side Functional
Groups
Hyperbranched /
Multifunctional
Hybrids with Inorganic & Biopolymers Functional Colloids
Modified Surfaces
Composition
Topology
Functionality
Molecular Composites
26

Isocyanates are highly reactive material. They can react with any active hydrogen
containing compound. Urethanes are formed when isocyanates react with polyols (Figure
2- 15).


Figure 2- 15 Urethane formation via the reaction of isocyanate with polyol

Polyisocyanates used for preparation PU coatings can be aromatic, aliphatic in
structure. The commonly used aromatic isocyanates are methylene diphenyl diisocyanate
(MDI) and toluene diisocyanate (TDI) (Figure 2- 16). Compared to TDI, MDI has a
lower volatility and thus lower toxicity.

Figure 2- 16 Aromatic isocyanate chemical structure

The commonly used aliphatic isocyanates include 1,6-hexamethylene
diisocyanate (HDI), isophorone diisocyanate (IPDI), bis(4-isocyanatocyclohexyl)methane
(H12MDI), and HDI isocyanurate (Figure 2- 17). In general, aromatic isocyanates react
faster than aliphatic isocyanates and are less expensive. Aliphatic isocyanates have better
color retention and exterior durability

R NCO R' OH
R
N OR'
H
O

NCO OCN
NCO
NCO
Methylene Diphenyl Diisocyanate (MDI)
Toluene Diisocyanate (TDI)
27



Figure 2- 17 Aliphatic isocyanate chemical structure

The polyols for PU coating are usually liquid with at least two hydroxyl groups.
Such polyols include polyester polyol, polyether polyol, and acrylic polyol. Polyester
urethane coatings are known for their chemical and solvent resistance, flexibility,
superior adhesion, and abrasion and corrosion resistance. This broad range of properties
is the result of the combination of soft (polyester) segments, which are responsible of the
elasticity of the coating, and the hard (polyurethane) segments, which supply the strength
of the films
78
.
The reaction rates of urethane formation decrease in the following order: primary
alcohols > secondary alcohols > 2-alkoxyethanols > 1-alkoxy-2-propanols > tertiary
alcohols. Aromatic isocyanates react faster than aliphatic isocyanates. In general, it is
normal to have high -NCO to -OH ratio (1.1:1.0), which produces harder and more
solvent resistant coatings.
34



OCN
NCO
NCO OCN
H
12
MDI
OCN
NCO
IPDI
N N
N O O
O
HDI
NCO
NCO
OCN
12
12
12
HDI isocyanurate
28

2.5 Non-isocyanate polyurethanes (NIPU)
Polyurethane coatings have wide applications in wood, automotive, industrial, and
coil coatings due to their high elasticity, toughness, and abrasive properties. Typically,
polyurethanes are obtained by the reactions of polyisocyanates with polyols. Usually
polyester, polyether, or polycarbonate is used as polyol reagent. The isocyanate is either
aliphatic or aromatic. Isocynates are toxic material. Exposure to isocyanate can result in
health effects such as skin irritation
79
. Also phosgene is a more toxic material, which is
used for preparation of the isocyanate.
Alternately, It was known that the carbamate group can be synthesized by the
reaction of the primary amine with cyclic carbonate
80, 81
. This provides a useful way to
obtain non-isocyanate polyurethanes (NIPU). Such non-isocyanate polyurethane was
prepared from the reaction of five-member ring cyclic carbonates oligomers with
diamines. Reaction products contain hydroxyl group in the -position
82
. This leads to the
intermolecular hydrogen bonds formation in the NIPU. Intramolecular hydrogen bonds
are formed within the structure of poly (hydroxy-urethane)s via the hydroxy group at the
-carbon atom and carbonyl group of the polyurethane chain (Figure 2- 18):

Figure 2- 18 Intramolecular hydrogen bonds formation in the NIPU
The hindrance of the carbonyl oxygen atom considerably lowers the susceptibility
of the urethane group to hydrolysis. Moreover, polyurethanes exhibiting intramolecular

R
O O
N
O
H
O
....
H
29

hydrogen bonds display chemical resistance up to twice greater in comparison with
polyurethanes of similar chemical structure without such bonds. The tensile strength of
non-isocyanate polyurethanes are similar to those of conventional isocyanate
polyurethanes, but display chemical resistance of 3050% higher and have significantly
reduced permeability.
These polyhydroxyurethanes show some useful characteristics, such as high water
absorption and thermal stability, because of the existence of the hydroxyl groups as well
as no contamination of thermally unstable biuret and allophanate units
83
.
2.5.1 Mechanism for NIPU preparation
The kinetic features of the interaction of cyclic carbonate groups with amino
groups were studied by Garipov et al
84
. The proposed 3-stage reaction mechanism is
shown in Figure 2- 19. The first stage is the nucleophilic attack of amine on cyclic
carbonate. Amine attacks the carboxyl group in cyclic carbonates resulting in the
formation of a tetrahedral intermediate. The second stage is the deprotonation of
tetrahedral intermediate. The tetrahedral intermediate is attacked by another amine
resulting in the removal of hydrogen ions. The last stage is the formation of final product.
The carbon-oxygen bond is broken, which is favored by the strong electron-withdrawing
effect of nitrogen atoms. The new generated alkyl-oxygen ion combines with hydrogen
ions, resulting in a rapid formation of the product.
30


Figure 2- 19 Mechanism for reaction between cyclic carbonate and amine
The reactivity of the amine towards cyclic carbonate could be accelerated by
using protogenic solvents. When protogenic solvents is used for the reaction, the first
stage occurs relatively rapidly due to the increase in the positively. The presence of the
electron withdrawing substituent in the alkylene carbonates, which increases the
electrophilicity of the carbonyl carbon, could also increase the reactivity of the reaction.
The reaction can also be effectively catalyzed by use of triethylamine, piperazine,
tetrabutylammonium bromide, glacial acetic acid, methanesulfonic acid
85
.
In most cases, five-member cyclic carbonates were used to react with aliphatic
amines to form the product with a -hydroxy-urethane (-hydroxy-carbamate) group and
no CO
2
is eliminated
86, 87, 88
. The reaction of mono-substituted 1, 3-dioxolan-2-one with
primary aliphatic amines leads to -hydroxy- urethanes with two isomeric structures in
the position of the hydroxyl group (Figure 2- 19). Studies on the distribution of isomers
showed that the product consists of 7075% of isomer bearing secondary hydroxyl group

HN
O O
O
R
R"
R'
+ O O
R
O
N
H
R'
R"
HN
R"
R'
H
2
N
R"
R'
O O
R
O
N
R'
R"
O O
R
O
N
R'
R"
(a)
(b)
(b)
(a)
R N
O
O
R'
R"
R
N
O
O
R"
R'
+ H
+
+ H
+
R N
OH
O
R'
R"
R
N
OH
O
R"
R'
O O
R
O
N
H
R'
R"
+
+
(2)
(1)
(3)
31

and 2530% of isomer bearing primary hydroxyl group
87, 89, 90
. At temperature higher
than 100
o
C the -hydroxy-urethanes react with another molecule of the amine to form
disubstituted urea. The investigations of the model reaction of 4-phenoxymethyl-1,3-
dioxolan-2-one show that in the formation of -hydroxy-urethane linkages mainly
primary aliphatic amines take part
91
. In contrast, aromatic amines react with five-
membered cyclic carbonates yielding aliphatic-aromatic amines accompanied by CO
2

elimination
87
.
2.5.2 Reactants for NIPU preparation
Amines, as one of the key reactants for preparation of NIPU, are usually
commercial available products. Amines could be either small molecules such as
ethylenediamine and isophorone diamine, or oligomers such as polyoxypropylene
diamine and JEFFAMINE amines. Cyclic carbonates are another key reactants for
preparation of NIPU. The Figure 2- 20 list the commonly used cyclic monomers structure,
which include mono-, bi-, tri-, and functional cyclic carbonate
92, 93
.
32


Figure 2- 20 Typical cyclic carbonate monomers structure
Five-member cyclic carbonates can be synthesized via several methods. The most
common involves the reaction of an oxirane with carbon dioxide
94
. This reaction is
highly facile and can be conducted at both atmospheric and elevated pressures with high
yields
95
. Rokicki et al
96
conducted the reaction of an oxirane bearing an ammonium
substituent with CO
2
under atmospheric pressure. This reaction is frequently used to
convert epoxy resins to cyclic carbonate resins
92
. Such reaction could be accelerated by
using different catalysts such as LiBr, tetrabutylammonium bromide (TBAB)
97
. The
catalysts for the reaction of epoxides and carbon dioxide had been reviewed
98
. Several
proposed reaction mechanisms were reviewed, and quaternary onium salt was found to be
the effective catalyst at atmospheric pressure of CO
2
. The proposed mechanism is shown
in Figure 2- 21.

O O
O
O O
O
R
O
O O
O
O O
CH
2
O OCH
2
CH
2
O OCH
2
CH
2
O CH
2 OCH
2
4
CH
2
OCO CH
2 COOCH
2
4
R =
a:
b:
c:
d:
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O O
O
O
O
O
O
O
O
O
O
O
Mono-Cyclic Carbonate
Bi-Cyclic Carbonate
Tri-Cyclic Carbonate
Functional Cyclic Carbonate
33


Figure 2- 21 Mechanism for quaternary onium salt catalyzed reaction between
oxirane and CO
2

98

Cyclo-carbonated soybean oil (CSBO) obtained from the reaction of epoxidized
soybean oil (ESBO) and CO
2
has aroused research interest for preparing NIPU, because
the ESBO is a renewable resource with low price. Rokicki et al
99
had reported that the
epoxy group conversion can be 98% after 120 hours reaction. The reactants ratio is 100g
ESBO + 0.4g 18-crown-6 + 0.6g KI, and no solvent was used. The reaction progress was
monitored by means of FTIR and 1H NMR as well as by epoxy number determination.
The disadvantage of the method is the use of the 6 MPa pressure. Wilkes et al
97
had
reported that the epoxy group conversion was assumed to be 100% in 70 hours which
was monitored by the FTIR. The reaction was using ESBO (200 g) and dried
tetrabutylammonium bromide (13.52 g; 5 mol% with respect to epoxy groups) and
carried out at 110C. No solvent was used. Other catalysts such as NaI, LiBr, and
benzyltrimethylammonium bromide showed very low to medium conversions under the
same condition because of the bad solubility in ESBO. The advantage is that the reaction
was carried out under atmospheric pressure. And the disadvantage of the method is the

CO
2 M X
O
O
X
X
OPh
O
M
OPh O
O
M
O
O O
OPh
O
M X
34

use of large amount of the catalyst, and the conversion rate was determined by FTIR
which can be used for a rough assessment, but not as a precise parameter for calculating
degree of conversion of epoxy to carbonate groups. In Javnis study
100
, less amount of
tetrabutylammonium bromide (TBAB) catalyst was used. The catalyst concentration is
0.025 mol or 3.4 g catalyst /100 g ESBO. The reaction of ESBO with CO
2
was carried
out in different conditions by varying the reaction parameters including temperature and
pressure. The progress of conversion of epoxy to carbonate groups was monitored by
FTIR, GPC, viscosity, and epoxy oxygen content (EOC).
2.5.3 Preparation of NIPU
Various non-isocyanate polyurethane (NIPU) can be prepared by selecting
different kinds of amines and cyclic carbonates starting materials. Linear NIPU can be
obtained if bifuntional starting materials are selected, and crosslinked NIPU can be
obtained if multi-functional starting materials are selected.
2.5.3.1 Linear NIPU
Linear polyurethanes can be obtained by the reaction of bifunctional five-
membered aliphatic cyclic carbonates with diamines (Figure 2- 22)
101
. In this method, in
contrast to the production of typical commodity polyurethanes, no toxic isocyanates are
used. The poly (hydroxyurethane)s with M
n
around 20,000 were prepared by the
polyaddition of bis (cyclic carbonate) and diamine in the DMSO solvent at 70
o
C or 100

o
C for 24h
101
. The bis (cyclic carbonate)s were prepared in the lab by the reaction of
bis(epoxide)s and atmospheric pressure of CO
2
in the presence of catalyst at 100
o
C for
3days. The polyaddition of bis (cyclic carbonate) and diamine shows high
35

chemoselectivity, and can be performed in the presence of water, alcohol, and esters.
Also, bis (cyclic carbonate) bearing ester group were used as a monomer to react with
amine to form poly (hydroxyurethane)s without aminolysis of the ester group. The poly
(hydroxyurethane) bearing the more secondary hydroxyl group is the major product. In
another article
83
, the model reaction was carried out by the reaction of bifunctional cyclic
carbonate with diamine to investigate the ratio of secondary alcohol to primary alcohol
moiety in the polyhydroxyurethane. In this model reaction, the equiv of 2,2-bis[p-(1,3-
dioxolan-2-one-4-yl-methoxy) phenyl]propane (B5CC) reacts with dioxa-1,12-
dodecanediamine (DODDA) in dimethyl sulfoxide (DMSO) at 70 C for 30 days. The
product polyhydroxyurethane contains the secondary alcohol moiety dominantly.


Figure 2- 22 Reaction of bis-cyclic carbonate with diamine
101

Amino acid/alcohol such as L-lysine and L-lysinol were chosen as highly
functionalized diamine to react with bifunctional five-membered cyclic carbonate to
afford optically active poly(hydroxyurethane)s with M
n
of 11,000-24,000. When the L-
Lysine was chosen as diamine, the reaction was carried out in N,N-dimethylacetamide
(DMAc) solvent in the presence of 1 equiv of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
or 2 equiv of sodium hydride at 70
o
C for 24 h to afford polyurethane bearing both

H
2
N R NH
2
n
R' O
O
O
O
O
O
O
O
H
N
R
H
N O O
O
OH
R' O O
O
OH
n
36

hydroxyl and carboxyl group. When the L-lysinol was chosen as diamine, the reaction
was carried out in N-methylpyrollidone (NMP) at 70
o
C for 24 h to afford polyurethane
bearing only hydroxyl group. These polyurethanes can be crosslinked to form
corresponding gels by cupric acetate, sodium tetrahydroborate, and titanium
tetraisopropoxide
102
.
A series of linear non isocyanate polyurethanes with M
n
of 6,000-9,000 and
relatively low PDI around of 1.5 were obtained by the polyaddition of
phenoxycarbonyloxymethyl ethylene carbonate with diamines
103
. These reactions were
carried out in N,N-dimethylacetamide (DMAc) at room temperature for 20h. The
monomer phenoxycarbonyloxymethyl ethylene carbonate was synthesized from the
phenyl chloroformate with glycerol carbonate which was prepared from the glycerol with
ethylene carbonate.
The linear non-isocyanate polyurethanes could be synthesized from the reaction
of the bis(cyclic carbonates) with diamines in aqueous media
104
. The results showed that
the bis(cyclic carbonates) with higher hydrophobilicity gave the polyhydroxyurethane in
higher yields, and the diamine with stronger nucleophilicity gave the
polyhydroxyurethane in higher yields. These suggest that the hydrophobilicity to protect
the carbonate from hydrolysis and sufficient nucleophilicity of the diamine are the
important factors to get polyhydroxyurethane in aqueous media. This method is
potentially applicable to prepare polyurethane emulsion by an environmentally benign
procedure.
The linear non isocyanate polyurethanes can also be synthesized from the one-pot
reaction of the bisepoxide, carbon dioxide and diamines
105
. The bis(cyclic carbonates)
37

was prepared from the reaction of bisphenoal A diglycidyl ether with carbon dioxide in 1-
Methyl-2-pyrrolidinone (NMP) at 100
o
C for 24h in the presence of LiCl or LiBr with
quantitative yield. After this, 1,12-diaminododecane(DAD) was added into this system,
and the mixture was stirred at 70
o
C for 6h to obtain polyhydroxyurethane with Mn of
around 11,000 and Tg of 31.18
o
C. When a bifunctional cyclic carbonate containing a
quaternary ammonium group was used in the reaction with diamines, a polyurethane-
ionomer exhibiting potential bacteriostatic properties was obtained
106,107
.
2.5.3.2 Crosslinked NIPU
A network of non-isocyanate polyurethanes can be obtained when multifunctional
cyclic carbonate oligomers (Figure 2- 23) are used in the reaction with multifunctional
primary amines
108
.

Figure 2- 23 Multifunctional cyclic carbonate oligomers structure
A network of non-isocyanate polyurethane can also be obtained from reaction of
linear polyurethanes bearing side hydroxyl groups with diisocyanate or aluminum
alkoxide
101
. When a highly functionalized diamine such as l-lysine is used for the

O
O
O
O
O
O
O
O
O
O
n
n
O
O
O
O
O
n
O
O
O
O
O
O
O
O
O
O
O
O
n
38

polyurethane synthesis, the resulting polymer contains additionally carboxyl groups
besides primary and secondary hydroxyl groups (Figure 2- 24)
102
.



Figure 2- 24 Reaction of l-lysine with biscyclic carbonate
102

The polyurethanes containing carboxyl and hydroxyl groups reacted with cupric
acetate, sodium tetrahydroborate, and titanium tetra-iso-propoxide to afford the
corresponding crosslinked gels immediately. These metallic gels are expected to be novel
optically active catalysts.
A network of polyurethane could also be formed from reaction of the amine
terminated nonisocyante polyurethane and epoxy. The amine terminated non-isocyanate
polyurethane was prepared from the reaction of excess diamine and biscyclic carbonate.
It has been reported that several mono- and bis(cyclic carbonates) were used to modify
the polyamine triethylenetetramine (TETA)
109
. The modified amine curing agents
containing -hydroxyurethane linkage were viscous liquids of a colouring from intense
yellow to orange. The presence of -hydroxyurethane groups in the modified amine
curing agent has main two effects on the curing system. The first one is to increase the
curing reactivity because of the formation of the hydrogen bond, weakening the C-O

O
O
O
O
O
O
O
O
H
N O O
O
OH
O O
O
OH
n
H
2
N NH
2
COOH
HCl
H
N
COOH
n
39

bond in the oxirane ring. The second one is to decrease the density of the crosslinking
because some protons are consumed in the reaction with cyclic carbonates and the
protons in the urethane linkage are inactive.
40

CHAPTER III

POLYESTER/POLY(METH)ACRYLATE BLOCK COPOLYMERS BY COMBINED
POLYCONDENSATION/ATRP: CHARACTERIZATION AND PROPERTIES

3.1 Abstract
Polyester/poly(meth)acrylate block copolymers are synthesized using a
combination of polycondensation and ATRP. All block copolymers are characterized by
means of NMR and GPC. Agreement between theoretical molecular weights of the
polymers with observed GPC values suggests controlled polymerization. In the case of
unsaturated-polyester-based block copolymers the main chain double bond in the
polyester backbone remains almost unaffected during ATRP. The unsaturated block
copolymers are crosslinkable and can form networks upon photoirradiation in the
presence of a suitable photoinitiator. These copolymers might be interesting candidates
for coatings with better overall properties than those based on neat polyesters.
3.2 Introduction
Polyesters are a class of polymers widely used in coating applications and are
generally synthesized by (i) polycondensation reaction of various diacid and diols and, (ii)
ring-opening polymerization (ROP) of the parent cyclic esters. The main
41

drawback of these polyesters is their poor hydrolytic/oxidative stability. In order to
improve the properties modification of polyester by preparing block copolymer is
desirable.
Significant progress has been made in the field of living free-radical
polymerization including nitroxide-mediated stable free-radical polymerization,
110, 111

atom-transfer radical polymerization (ATRP)
112, 113, 114, 115
and reversible
addition/fragmentation chain transfer (RAFT) polymerization.
116, 117
All these controlled
polymerizations can be used to synthesize polymers and copolymers. ATRP has already
been proven a powerful tool to synthesize polymers that are not accessible through
conventional radical polymerization of vinyl monomers. A combination of ring-opening
methatesis polymerization (ROMP) with ATRP was prepared for the synthesis of various
block copolymers of caprolactone.
118
For example, Mecerreyes et al. reported random
and block copolymers of caprolactone and methyl methacrylate by ATRP.
119

Detrembleur et al. reported homopolymerization and random and block copolymerization
of -bromo--caprolactone.
120
Yuan et al. reported controlled polymerization of 5,6-
benzo-2- methylene-1,3-dioxepane (BMDO) by ATRP.
121
Schappacher et al. synthesized
diblock and triblock copolymers of caprolactone and methyl methacrylate (MMA).
122

Polyesters synthesized by polycondensation reactions are widely used in coating
applications and for protection of surfaces. Most of the polyesters used in coatings have
relatively low molecular weights and are amorphous and branched. These types of
polyesters are cost-effective and easily synthesized by polycondensation reaction
between various commercially available diols and diacids in bulk conditions and are
widely demanded by industry. In general, these type of polyesters are crosslinked by the
42

reaction with triisocynates or with melamine/formaldehyde (MF) resins and used for
coating applications.
123, 124

High-molecular-weight polyesters or polyester/polyurethanes have appreciable
mechanical properties such as high tensile strength together with flexibility. But the
presence of ester linkages in the backbone of polyesters makes them vulnerable to
acids/bases. On the other hand, poly(meth)acrylates have better abrasion resistant, and
hydrolytically stable with superior mechanical properties. Hence, to improve the
hydrolytic/oxidative stability and to achieve chemical abrasion resistance properties it is
highly desirable to prepare copolymers of polyesters and poly(meth)acrylates. Previously,
crosslinked polyester networks were synthesized by a two-step synthesis. First, synthesis
of polyester with acrylic or methacrylic chain-ends and then crosslinking by the reaction
with reactive diluents upon photo-irradiation.
125
However, this process may also produce
undesirable homopolymers and sometimes phase-separated polymers with inferior
properties.
To the best of our knowledge, there is no report of the synthesis of block
copolymers of polyesters with (meth)acrylates in which polyesters are synthesized by
reacting small-molecular-weight diacids and diols. In this work, we demonstrate the
synthesis of different block copolymers of unsaturated and saturated polyesters (UPE and
SPE, respectively) with (meth)acrylates with well-defined molecular weight and narrow
polydispersity by combination of condensation polymerization and ATRP. This work
also shows that the unsaturation present in the main chain of the polyesters is almost
unaffected during ATRP and the synthesized unsaturated polyester/(meth)acrylate block
copolymers can form crosslinked networks upon irradiation.
43

3.3 Materials
MMA, ethyl methacrylate (EMA), ethyl acrylate (EA), butyl acrylate (BA), 2-
ethyl hexyl acrylate (EHA), basic aluminium oxide (Aldrich) were passed through a basic
alumina column and then distilled under reduced pressure and stored under nitrogen
atmosphere. Acetone (GR, Fisher Scientific) was distilled before use. 2-Butanone, 1-
propanol, p-xylene, isophthalic acid (IPA), maleic anhydride (MA), 1,6 hexanediol (HD),
neopentyl glycol (NPG), dibutyltin oxide (DBTO), 2,2-bipyridyl (bpy, 98%), CuBr (98%)
and CuCl (98%), methylene chloride, triethylamine (Et
3
N), bromoisobutyryl bromide
(EbiB), bromopropionyl bromide (MBrP), magnesium sulfate (MgSO
4
), tetrahydrofuran
(THF), pentamethyldiethylenetriamine (PMDETA) were used as received (all from
Aldrich). Me
6
TREN tris(2-aminoethyl)amine(TREN) was synthesized according to the
literature.
126

3.4 Instrumentation and characterization
The FT-IR spectra of the polyesters and macroinitiators were measured on a
Nicolet 380 FTIR spectrophotometer. The results were analyzed using OMNIC software.
The NMR spectrum of all the polyesters, macroinitiators and block copolymers
were recorded on a Varian Mercury 300MHz spectrophotometer. All the NMR spectra
were measured by dissolving the samples in CDCl
3
.
Molecular weight and molecular weight distribution of all the polyesters,
polyester-based macroinitiators and polyester-based (meth)acrylate block copolymers
were determined in a Waters 1515/2414 gel permeation chromatography (GPC)
44

instrument equipped with a refractive index detector using THF as eluent at a flow rate
0.5mLmin
1
and polystyrene as a calibration standard at room temperature.
The glass transition temperature of all the polyesters and polyester-based block
copolymers was measured in a TA instrument DSCQ 1000 model. All the samples were
heated from 90 to 130C at a heating rate 10Cmin
1
under nitrogen atmosphere.
TA Instrument DSC-Q1000 (Photo DSC), equipped with a Novacure N2001-A1
as UV-light source, was used to investigate the heat flow of curing the product. The
wavelength ranged from 250 to 600nm and the initiation light source was a 100W high-
pressure mercury short-arc lamp of intensity 250mWcm
2
.
Acid number (Aac) was determined according to ASTM standard D 1639-90.
Two gram of resin was measured and dissolved in 50 g of an equal mixture of acetone. A
phenolphthalein indicator solution was prepared at 0.5 wt-% in methanol. One milliliter
of the phenolphthalein indicator was added to the acetone/ethanol solution. The sample
was titrated with 0.1 N solution of potassium hydroxide in methanol until the solution
obtained a slight pink coloration. The potassium hydroxide solution was prepared by
measuring approximately 2.81 g of KOH and dissolved in ethanol in a 500 mL graduated
flask. At a given moment during the hydrolysis the acid number was calculated with the
following equation

(3-1)

where N and V represented the normality (mol/L) of the basic solution made from
potassium hydroxide (KOH), and the volume (mL) of KOH solution required to
neutralize the desired amount of oligoester, m, measured in grams.

45

3.5 Synthesis
In this synthesis part, hydroxyl terminated saturated and unsaturated polyesters
were synthesized. These polyesters were used to prepare corresponding macroinitiators.
These macroinitiators wre used to polymerize different kinds of (meth) acrylates by
ATRP.
3.5.1 Synthesis of IPAMA-HDNPG UPE
To synthesize hydroxy-terminated polyester, excess diol was used. The molar
ratio of diol to diacid was 10:9. A representative example of the synthesis of hydroxyl-
terminated polyester is as follows. IPA (135.5g, 0.82mol), MA (80g, 0.82mol), HD
(132.4g, 0.9mol) and NPG (94.4g, 0.9mol) were taken in a 500mL four-necked round-
bottom flask which was equipped with a mechanical stirrer, a gas inlet, a temperature
controller, a Dean-Stark trap and a condenser. The reaction proceeded under argon to
minimize oxidative degradation. To accelerate the reaction, 0.4% (by weight) of DBTO, a
trans-esterification catalyst, was used. 0.1% Hydroquinone was added as a radical
scavenger to prevent the polymerization of MA. Then 3wt% xylene was also added into
the reaction mixture to remove water from the resin as azeotropic mixture. The reaction
temperature was carefully controlled using a temperature controller and a thermocouple
in order to minimize evaporation of diol. The temperature of the mixture was increased
from 20 to 150C at a rate of 4.3Cmin
1
, and then from 150 to 210C at a rate of
0.25Cmin
1
. The final temperature was held until the resin had an acid number
measured by titration less than or equal to 10mg KOH per g resin. Other polyesters were
also synthesized using similar procedure. The hydroxyl number of polyesters was
46

determined according to ASTM (ASTM D 1957-86). NMR chemical shifts were =8 (H
from IPA), 6 and 7 (CH=CH in the polyester backbone) 4.10 (-OCH
2
from polyester
backbone), 3.6 (HOCH
2
of end group) and 2.25 (-CH
2
attached to C=O), 1.7
(O=CCH
2
CH
2
, OCH
2
CH
2
) 1.4 (-OCH
2
CH
2
CH
2
), respectively. Mn and PDI of the block
copolymer were 1500 and 1.74, respectively.
3.5.2 Synthesis of adipic acid/1,6-hexanediol (AA-HD) SPE
Similar procedure was used for the synthesis of various SPEs. A representative
example of synthesis of hydroxyl-terminated polyester is as follows.
The molar ratio of diol to diacid was 5:4. AA (150g, 1.026mol) and 57g HD
(151.5g, 1.28mol) were added to a 500mL four-necked round-bottom flask which was
equipped with a mechanical stirrer, a gas inlet, a temperature controller, a Dean-Stark
trap and a condenser. The reaction proceeded under argon to minimize oxidative
degradation. To accelerate the reaction, 0.4wt% of DBTO, a trans esterification catalyst,
was used. Then, 3wt% of xylene was also added into the reaction mixture to remove
water from the resin as azeotropic mixture. The reaction temperature was carefully
controlled using a temperature controller and a thermocouple in order to minimize
evaporation of diol. The temperature of the mixture was increased from 20 to 150C at a
rate of 4.3Cmin
1
, and then from 150210C at a rate of 0.25Cmin
1
. The final
temperature was held until the resin had an acid number measured by titration less than or
equal to 10mg KOH per g resin. Other polyesters were also synthesized using similar
procedure. The hydroxyl number of polyesters was determined according to ASTM
(ASTM D 1957-86). NMR chemical shifts were =4.10 (-OCH
2
from polyester
47

backbone), 3.6 (HOCH
2
of end group) and 2.25 (-CH
2
attached to C=O), 1.7
(O=CCH
2
CH
2
, OCH
2
CH
2
) and 1.4 (-OCH
2
CH
2
CH
2
), respectively.
3.5.3 Synthesis of UPE-based difunctional macroinitiator (UPE1) for methacrylate
polymerization
A representative example of the synthesis of the polyester-based difunctional
macroinitiator is as follows. UPE (88.5g, 0.052mol) was taken in a 1 L three-necked
round-bottom flask and dry methylene chloride (500mL) was added into it. The whole
mixture was kept on in an ice bath and stirred over a magnetic stirrer under nitrogen
atmosphere. The temperature of the mixture was maintained at less than 5C. Then Et
3
N
(22mL, 0.17mol) was added. EBiB (22mL, 0.17mol) was added dropwise into the
mixture. The whole reaction was stirred overnight. Then the mixture was filtered to
remove the salt produced by the esterification reaction. Then the solution was washed
with saturated solution of NaHCO
3
in water followed by distilled water (three times) to
remove unreacted EBiB and Et
3
N. Then, MgSO
4
was added to remove trapped water and
filtered. Dichloromethane was removed by rotary evaporator at room temperature. The
product was characterized by IR and NMR spectroscopy.
3.5.4 Synthesis of UPE-based difunctional macroinitiator (UPE2) for acrylate
polymerization
UPE (52.5g, 0.03mol) was taken in a 500mL three-necked round-bottom flask
and dry methylene chloride (300mL) was added. The whole mixture was kept in an ice
bath and stirred over a magnetic stirrer under nitrogen atmosphere. The temperature of
the mixture was maintained at less than 5C. Next, Et
3
N (14mL, 0.10mol) was added.
48

MBrP (11.5mL, 0.17mol) was added dropwise into the mixture. The whole reaction was
stirred for overnight. Then the mixture was filtered to remove the salt produced by
esterification reaction. Then, the solution was washed with saturated solution of NaHCO
3

in water followed by distilled water (three times) to remove unreacted EbiB and Et
3
N.
Then, MgSO
4
was added to remove trapped water and filtered. Dichloromethane was
removed by rotary evaporator at room temperature. The product was characterized by IR
and NMR spectroscopy. In IR spectroscopy the broad peak around 3400cm
1
for -OH
group disappeared which confirmed the synthesis of the macroinitiator. The NMR peak at
=3.6 (for end -CH
2
OH) disappeared and mergeed with the one at =4.1 (for -OCH
2
),
thus confirming the completion of the esterification reaction.
Along similar routes, SPE1- and SPE2-based macroinitiators were synthesized by
esterification reactions of hydroxyl-terminated SPEs with EBiB and MBrP, respectively.
3.5.5 Synthesis of poly(MMA)-block-UPE1-block-poly(MMA) (PMMA-b-UPE1-b-
PMMA)
A representative example of synthesis of triblock copolymers via ATRP is as
follows. In a nitrogen-purged 25mL single-necked round-bottom flask, provided with a
B-19 standard joint and a stir bar were added CuBr (0.28g, 2mmol) and Me
6
TREN
(0.48g, 2mmol), respectively. Nitrogen purging was continued for 10min, after which
the tube was closed with a rubber septum that was secured by a Cu wire. MMA (5mL,
50mmol), acetone (2.5mL), all purged separately with nitrogen were next injected into
the tube with a nitrogen purged gas-tight syringe. The admixture was sonicated for 2min.
A deep brown color resulted. UPE1 (1.7g, 1mmol) was then injected. The tube was then
put in an oil bath maintained at 50C. The polymerization mixture was stirred
49

magnetically. At suitable time intervals aliquots (1mL) of the reaction mixture were
withdrawn, diluted with 1mL THF and poured into hexane. The polymers were isolated
by centrifugation, dried, redissolved in THF and reprecipitated into hexane. They were
finally dried in a vacuum oven at 50C for 48h. After 1.5h conversion was 90%. The
Mn and PDI values were 6400 and 1.90, respectively. A similar polymerization
procedure was used for the polymerization of EMA.
1
H NMR chemical shifts were
=3.6 [-OCH
3
from PMMA], 0.8 and 1.0 [-CH
3
of PMMA]. A similar polymerization
procedure was followed to polymerize EMA.
3.5.6 Synthesis of poly(BA)-block-UPE2-block-poly(BA) (PBA-b-UPE2-b-PBA)
CuBr (0.28g, 2mmol), Me
6
TREN (0.48mL, 2mmol) and UPE2 (1.7g, 1mmol)
were taken in a reaction vessel, already purged with nitrogen and the vessel was sealed
with a rubber septum. Into the vessel, previously purged BA (5.6mL, 39mmol) and
acetone (2.8mL) was added by using a syringe. The reaction mixture was stirred for
3min at room temperature and then was placed in an oil bath at 50C. After 1h, the
conversion was 70% and Mn and PDI were 5000 and 2.07, respectively. A similar
polymerization procedure was used for EA and EHA. Chemical shifts of =3.9 [-OCH
2

from PBA], 0.8 and 1.0 [-CH
3
of PBA] were observed.
3.5.7 Synthesis of poly(MMA)-block-poly(BA)-block-UPE2-block-poly(BA)-block-
poly(MMA) (PMMA-b-PBA-b-UPE2-b-PBA-b-PMMA)
The difunctional PBA-b-UPE2-b-PBA macro-initiator (1.8g, 0.4mmol) (Mn=5000,
PDI=2.07) was taken in a round-bottom single-necked flask, dissolved in acetone (1g)
and purged with nitrogen. MMA (2g, 20mmol) was nitrogen-purged and injected into
50

the vessel. Me
6
TREN (0.19mL, 0.8mmol) and CuCl (0.079g, 0.8mmol) were next
added under nitrogen. The mixture was sonicated for about 2min and the vessel was
placed in an oil bath at 50C and the solution was stirred. A conversion of 40% was
reached in 1h. Mn and PDI of the block copolymer were 8 100 and 2.4, respectively.
3.5.8 Synthesis of poly(BA)-block-poly(MMA)-block-UPE1-block-poly(MMA)-block-
poly(BA) (PBA-b-PMMA-b-UPE1-b-PMMA-b-PBA)
The difunctional PMMA-b-UPE1-b-PMMA macro-initiator (2.36g, 0.4mmol)
(Mn =6400, PDI=1.9) was taken in a round-bottom single-necked flask, dissolved in
acetone (1g) and purged with nitrogen. BA (2g, 15.6mmol) was nitrogen-purged and
injected into the vessel. Me
6
TREN (0.19mL, 0.8mmol) and CuBr (0.114g, 0.8mmol)
were next added under nitrogen. The mixture was sonicated for about 2min and the
vessel was placed in an oil bath at 50C and the solution was stirred. A conversion of 90%
was reached in 1.5h. Mn and PDI of the block copolymer were 12 900 and 2.2,
respectively.
3.5.9 Bulk ATRP of MMA using UPE-based macroinitiator
A representative example of synthesis of triblock copolymers in bulk condition
via ATRP is as follows. In a nitrogen-purged 25mL single-necked round-bottom flask,
provided with a B-19 standard joint and a stir bar were added UPE1 (1.7g, 1mmol),
CuBr (0.28g, 2mmol) and Me
6
TREN (0.48g, 2mmol), respectively. Nitrogen purging
was continued for 10min, after which the tube was closed with a rubber septum which
was secured by a Cu wire. MMA (5mL, 50mmol), purged separately with nitrogen were
next injected into the tube with a nitrogen-purged gas-tight syringe. The admixture was
51

sonicated for 2min. A deep brown color resulted with complete dissolution of polyester.
The tube was then put in an oil bath maintained at 50C. The polymerization mixture
was stirred magnetically. Gelation occurred within 30min and the polymer was insoluble
in organic solvents.
3.5.10 Synthesis of poly(MMA)-block-SPE1-block-poly(MMA) (PMMA-b-SPE1-b-
PMMA)
In a nitrogen purged 25mL single neck round bottom flask, provided with a B-19
standard joint and a stir bar were added CuCl (0.4g, 4mmol), CuCl
2
(0.025g, 0.2mmol)
and bpy (0.13g, 8.8mmol), respectively. Nitrogen purging was continued for 10min,
after which the tube was closed with a rubber septum that was secured by a Cu wire.
MMA (10mL, 169mmol), acetone (10mL), all purged separately with nitrogen were
next injected into the tube with a nitrogen-purged gas-tight syringe. The admixture was
sonicated for 2min. A deep brown color resulted. SPE1 (3.8g, 2mmol) was then injected.
The tube was then put in an oil bath maintained at 50C. The polymerization mixture
was stirred magnetically. At suitable time intervals aliquots (1mL) of the reaction
mixture were withdrawn, diluted with 1mL THF and poured into hexane. The polymers
were isolated by centrifugation, dried, redissolved in THF and reprecipitated into hexane.
They were finally dried in a vacuum oven at 50C for 48h. After 5h conversion was
90%. Mn and PDI were 7 800 and 1.46, respectively. A similar polymerization procedure
was used for the polymerization of EMA. Chemical shifts of =3.6 [OCH
3
from
PMMA], 0.8 and 1.0 [-CH
3
of PMMA] were observed.
52

3.6 Results and discussion
The main objective of this work is the synthesis of varieties of block copolymers
containing poly(meth)acrylate and UPE and/or SPE with improved over all properties.
3.6.1 Synthesis of polyester-based block copolymers
UPE was synthesized via condensation polymerization using equimolar mixture
of diacid IPA and MA and mixture of excess diols, e.g., HD and NPG. Similarly
saturated hydroxyl telechelic polyesters were synthesized by simple condensation
polymerization between diacid and excess diol. (Meth)acrylate block copolymers of UPE
and SPE were synthesized via ATRP. Table 3- 1 summarizes the abbreviations,
composition, molecular weights and molecular weight distributions of hydroxyl-
telechelic polyesters synthesized by condensation polymerization.
Table 3- 1 Properties of hydroxyl-telechelic polyesters

Polyester

Diol :
Diacid
Acid #
(mg KOH/g
resin)
Hydroxyl #
(mg KOH/g
resin)

M
n
(g/mol)

PDI

Description
GPC NMR
IPAMA-
HDNPG
10 :9 8.2 125 1500 1700 1.74 CL
a)

AA-HD-A 5 :4 8.0 101 1700 1600 1.60 WS
b)

AA-HD-B 8 :7 6.0 110 2100 2100 1.60 WS
AA-HD-C 10 :9 9.5 130 2300 2400 1.70 WS
IPA-HD 5 :4 6.2 120 1500 1600 1.65 WS
PA-HD 5 :4 5.3 165 1100 1200 1.60 CL
AA-NPG 5 :4 4.0 180 1400 1500 1.60 CL
a) CL = Clear Liquid; b) WS = White Solid

Figure 3-1 shows the chemical structures of different diacids, diols and hydroxyl
functional representative UPE and SPE synthesized by simple condensation reactions.
53

The hydroxyl functional polyesters were converted to macroinitiators for the ATRP of
varieties of acrylates and methacrylates. For example, for acrylates polymerizations, the
polyesters were modified to macroinitiators the ends of which resemble the structure of
acrylate and for methacrylates polymerization the polyester were modified to
macroinitiators the ends of which resemble the structure of methacrylate.
127, 69, 128


Figure 3- 1 Chemical structure of diacids, diols and representative SPE and UPE

HO
OH
1, 6-Hexanediol (HD)
HO OH
Neopentyl Glycol (NPG)
COOH
COOH
Isophthalic Acid (IPA)
O
O
O
Phthalic Anhydride (PA)
HOOC
COOH
Adipic Acid (AA)
O
O O
Maleic Anhydride (MA)
O
O
O
O
H
O
O
H
n
HO
O
O
O O
O
O O
O
OH
n
6
6
AA-HD
IPAMA-HDNPG
54

Figure 3- 2 shows the general synthesis procedure of polyesters-based block
copolymers of poly(meth)acrylates [poly(meth)acrylate-block-UPE and/or SPE-block-
poly(meth)acrylate] starting from polyesters synthesis. The ATRP of various
(meth)acrylates monomers using polyesters-based macro-initiators was studied in terms
of molecular weights variations with monomer conversion and molecular weights
distributions.

Figure 3- 2 Synthesis of polyester-poly(meth)acrylates block copolymers.

OH
R
1
O
R
1
' O
R
1
O
O O
HO R
1
OH
R'
1
HOOC COOH
+
Br
R"
O
Br
NEt
3
CH
2
Cl
2
0~5
o
C
R"=H, CH
3
n
ATRP of (Meth)acrylate
Block Copolymer
HO R
2
OH R'
2
HOOC COOH
R
2
' O
R
2
O
H
O O
n
O
R
1
O
R
1
' O
R
1
O
O O
n
R
2
' O
R
2
O
O O
n
"R
O
Br
R"
O
Br
Either R
1
' or R
2
' is unsaturated
55

3.6.2 Synthesis of UPE-based block copolymers
ATRP of acrylates and methacrylates were conducted in acetone using
CuX/Me
6
TREN (X=Cl, Br) catalysts at 50C. Both CuBr/Me
6
TREN and
CuCl/Me
6
TREN catalyst systems produced block copolymers with controlled molecular
weight with active chain-end. The rate of ATRP with CuCl/Me
6
TREN catalyst is slower
than CuBr/Me
6
TREN. It was reported that the mixed-halide initiating system
(EBiB/CuCl) leads to much better control in ATRP of MMA using 4,4-di(5-nonyl)-2,2-
bipyridine (dNbpy) as the ligand.
69, 128
This was attributed to faster initiation by cleavage
of the weaker C-Br bonds in EBiB and slower propagation due to the polymer chain,
which predominantly contains stronger C-Cl bonds. In contrast to the reported work, the
present work shows that in case of acrylates polymerization where the macroinitiator
contains MBrP moiety gives better control with the CuBr/Me
6
TREN catalyst system than
that of CuCl/Me
6
TREN catalyst. This result might be attributed to a lesser tendency for
cleavage of the C-Br bonds in MBrP containing polyester chain ends and thereby forming
a secondary radical that is less stable than the tertiary radical generated from a
methacrylate-type initiator which contains EBiB chain ends. In the MBrP/CuCl system,
the difference in rate of initiation and rate of propagation is not so much prominent as in
EBiB/CuCl system, thereby rendering it a system of less importance for halogen
exchange.
Table 3- 2 summarizes the results of the ATRP of methacrylates (MMA and EMA)
and acrylates (BA, EA and EHA) using UPE-based macro-initiators. From the molecular-
weight data it can be observed that the theoretically calculated molecular weights are
close to those determined by GPC, suggesting controlled polymerizations.
56

Table 3- 2 Results of ATRP of different (meth)acrylates using UPE-based macroinitiators
Entry Catalyst system Block Copolymer
Conversion
a)

(%)
Mn (g / mol) PDI I
eff


Theor. GPC
1 CuBr/Me6TREN PEA-b-UPE2-PEA 75 16750 18000 2.2 0.93
2 CuCl/Me6TREN PEA-b-UPE2-PEA 75 13000 15300 2.15 0.84
3 CuBr/Me6TREN PBA-b-UPE2-PBA 70 12250 13500 2.25 0.9
4 CuCl/Me6TREN PBA-b-UPE2-PBA 80 13750 15500 2.22 0.88
5 CuBr/Me6TREN PEHA-b-UPE2-PEHA 80 13750 15000 2.3 0.91
6 CuCl/Me6TREN PEHA-b-UPE2-PEHA 70 12250 14300 2.3 0.85
7 CuBr/Me6TREN PMMA-b-UPE1-b-PMMA 75 16750 18000 2.25 0.93
8 CuCl/Me6TREN PMMA-b-UPE1-b-PMMA 80 13750 14550 2.08 0.94
9 CuBr/Me6TREN PEMA-b-UPE1-b-PEMA 80 17750 19300 2.18 0.91
10 CuCl/Me6TREN PEMA-b-UPE1-b-PEMA 76 13150 14000 2.12 0.93
11 CuCl/Me6TREN PMMA-b-UPE1-b-PMMA 50 3200 4700 2.25 0.78
12 CuCl/Me6TREN PEA-b-UPE2-PEA 51 4500 5550 2.13 0.81
13 CuCl/Me6TREN PBA-b-UPE2-PBA 52 4600 5350 2.18 0.82
14 CuCl/Me6TREN PEHA-b-UPE2-PEHA 52 4600 5550 2.12 0.82
15 CuCl/Me6TREN
PMMA-b-PEHA-b-UPE2-
PEHA-b-PMMA 30 6000 7600 2.4 0.78
a) Determined by means of gravimetry, I
eff
= Mn (theo)/Mn (GPC), UPE1 and UPE2 are
unsaturated polyester (IPA-MA-ND-NPG)-based macroinitiators, the chain-ends of
which resemble the structures of methacrylate and acrylate, respectively.
Figure 3- 3a shows representative kinetic plots of disappearance of MMA and
EMA in acetone at 50C using UPE1 as macroinitiator and CuBr/Me
6
TREN and
CuCl/Me
6
TREN as catalysts. In acetone the complex becomes soluble and thus good
control over polymerization was achieved. Figure 3- 3b shows representative kinetic plots
of disappearance of EA, BA and EHA in acetone at 50C. UPE2 was used as
macroinitiator and CuBr/Me
6
TREN was used as catalyst. Acetone was selected as a
57

solvent for both methacrylates and acrylates polymerization because: (i) the catalysts are
well soluble in acetone and (ii) the Cu(I)Me
6
TREN complex is stable (no
disproportionation) and thereby facilitates the ATRP of (meth)acrylates at 50C.
129, 130



Figure 3- 3 (a) Kinetic plots of ATRP of MMA (lines 1 and 2) and EMA (lines 3 and 4)
in acetone at 50
0
C using UPE1 as macroinitiator. Lines 1 and 3: CuBr/Me6TREN and
lines 2 and 4: CuCl/Me6TREN catalysts. (b) Kinetic plots of ATRP of EA (line 1), BA
(line 2) and EHA (line 3) using UPE2 macroinitiator in acetone and CuBr/Me6TREN
catalyst at 50
0
C

0 10 20 30 40 50 60 70 80 90 100 110 120 130
0.0
0.5
1.0
1.5
2.0
4
3
2
1
l
n
(
[
M
0
]
/
[
M
]
)
time (min)
a)

0 10 20 30 40 50 60 70 80 90 100 110 120 130
0.0
0.2
0.4
0.6
0.8
1.0
1.2

l
n
(
[
M
0
]
/
[
M
]
)
3
2
1
Time (min)
b)
58

The first order kinetic plots for monomer disappearance were linear for all the
polymerization which indicates constant radical concentration throughout the
polymerization and hence indicates controlled polymerization. Linear increase of
molecular weights and decrease of PDIs suggest control living polymerizations.
131, 132

Figure 3- 4 shows representative GPC chromatograms of (a) UPE1, (b) PMMA-b-
UPE1-b-PMMA tri-block copolymer and (c) PBA-b-PMMA-b-UPE1-b-PMMA-b-PBA
pentablock copolymer, respectively. Figure 3- 5 also shows representative GPC traces of
(a) UPE2, (b) PBA-b-UPE2-b-PBA tri-block copolymer and (c) PMMA-b-PBA-b-UPE2-
b-PBA-b-PMMA penta-block copolymers, respectively.

Figure 3- 4 GPC traces of (a) UPE1, (b) PMMA-b-UPE1-b-PMMA triblock copolymer
and (c) PBA-b-PMMA-b-UPE1-b-PMMA-b-PBA pentablock copolymers, respectively.


14 16 18 20
c. Mn=12400
PDI=2.20
b. Mn=6400
PDI=1.90
a. Mn=1750
PDI=1.74


I
n
t
e
n
s
i
t
y
Elution Volume (mL)
59


Figure 3- 5 GPC traces of starting (a) UPE2, (b) PBA-b-UPE2-b-PBA triblock copolymer
and (c) PMMA-b-PBA-b UPE2-b-PBA-b-PMMA penta-block copolymers, respectively
The symmetrical GPC chromatograms of block copolymers and the shifting to
high molecular weight side indicate efficient initiation of unsaturated polyesters-based
macroinitiators. There is an increase of PDI (2.4) of the penta-block copolymer of
PMMA-b-PBA-b-UPE2-b-PBA-b-PMMA was observed in compare to PDI (2.2) of
PBA-b-PMMA-b-UPE2-b-PMMA-b-PBA copolymer. This is attributed to the slow
initiation of triblock copolymer PBA-b-UPE2-b-PBA to initiate MMA polymerization.
The broadening of GPC trace of pentablock copolymer may be also due to the presence
of unreacted triblock macroinitiator with dead chain-ends.
Figure 3- 6 shows a representative NMR spectrum of (a) UPE1 macroinitiator, (b)
PMMA-b-UPE1-b-PMMA and (c) poly(EA)-block-UPE1-block-poly(EA) (PEA-b-
UPE1-b-PEA) copolymers, respectively. In the spectrum of the unsaturated polyester (not

14 16 18 20
c. Mn=7600
PDI=2.40
b. Mn=5000
PDI=2.07
a. Mn=1750
PDI=1.74


I
n
t
e
n
s
i
t
y
Elution Volume (mL)
60

shown), peaks at =7.5, 8.2 and 8.7 correspond to three different types of aromatic
protons coming from IPA, those at =6.2 and 6.8 correspond to double-bond presence in
the polyester backbone. Other peaks at =4.10 (-OCH
2
from polyester backbone), 3.6
(HOCH
2
of end group) and 2.25 (-CH
2
attached to C=O) are observed. In spectrum a, a
peak at =3.6 (HOCH
2
of end group) disappears and merges with the one at =4.10.
This shows complete esterification of the hydroxyl group in polyester. In spectrum b, the
peak at =3.6 corresponds to (OCH
3
) of PMMA and the ones at =0.8 and 1.0
correspond to -CH
3
from PMMA. In spectrum c, the peak at =3.8 corresponds to
(OCH
2
) of PEA and those at =0.8 and 1.0 correspond to -CH
3
from PEA.
upe13
8 7 6 5 4 3 2 1
Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
N
o
r
m
a
li
z
e
d
In
te
n
s
i
ty
O
O
O
O O
O
O O
O
O
n
6
6
Br
O
Br
O

upe12
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
N
o
r
m
a
li
z
e
d
In
te
n
s
i
ty
O
O
O
O O
O
O O
O
O
n
6
6
O
O
Br
O
O
Br
O
O
n n


b)
a)
61

upe18
9 8 7 6 5 4 3 2 1 0
Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
N
o
r
m
a
li
z
e
d
In
te
n
s
i
ty
O
O
O
O O
O
O O
O
O
n
6
6
O
O
Br
O
O
Br
O
O
n
n

Figure 3- 6 The NMR spectra of (a) UPE1 macroinitiator (b) PMMA-b-UPE1-b-PMMA
and (c) PEA-b-UPE2-b-PEA tri-block copolymers, respectively
In both triblock copolymers (see Figure 3-6b and c) peaks at =6.2 and 6.8 are
observed which clearly indicate that main-chain double bonds are present in the final
copolymer when the monomer conversion was essentially <70%. However, NMR spectra
of the UPE-based copolymers also suggest that the intensity ratio of protons attached to
the unsaturated carbons of maleic ester and aromatic proton signals decreases about 12%
than that of neat UPE suggesting formation of branched structure.
The successful solution-phase ATRP in presence of unsaturation is attributed to
the (i) much higher concentration of polymerizable monomer than unsaturation present in
the macroinitiator (relatively less reactive), (ii) mild reaction condition (50C) used in
the solution phase (25% acetone) ATRP and due to (iii) low radical concentration during
polymerization (ATRP). On the other hand, bulk ATRP of acrylates and methacrylates
using UPE-based macroinitiator resulted very fast polymerization with gelation and
disappearance of unsaturation. This is mainly due to high radical concentration and very
high conversion with in short reaction time (less than 10min).
c)
62

3.6.3 Synthesis of SPE-based block copolymers
Block copolymers of different SPEs were synthesized along the lines described
above. Different catalyst systems were employed for the ATRP of meth(acrylates).
Methacrylates polymerizations were carried out in acetone using CuCl/bpy catalyst. As
regards, the use of the CuCl/bpy instead of CuBr/bpy complex as catalyst, the later did
not go completely into solution in acetone. Block copolymer with higher polydispersities
were obtained when CuBr/bpy was used. On the other hand, in acetone using either
CuBr/PMDETA or CuCl/PMDETA catalyst, mixture was homogeneous initially but with
the progress of the reaction the mixture became heterogeneous. The kinetic plots were
nonlinear and the molecular weights of the polymer were much higher than the
theoretical values and PDIs were broad (PDI2).
Acrylate ATRP was conducted in bulk using CuBr/PMDETA catalyst. The
polymerization with CuBr/bpy catalyst was also controlled. The theoretical molecular
weights were close to experimental molecular weights and PDIs were 1.5. The rate of
polymerization was slower when CuBr/bpy was used as catalyst.
Table 3- 3 summarizes the results of the ATRP of methacrylates (MMA and EMA)
and acrylates (BA, EA and EHA) using SPE1 and SPE2 macroinitiators. From the
molecular weights and PDIs data it can be observed (Table 3- 3) that all the
polymerizations were well controlled and the theoretically calculated molecular weights
were close to those determined by GPC molecular weights. The lowering the PDIs of the
block copolymer in compare to mecroinitiator is attributed to the (i) controlled ATRP and
(ii) presence of small amount of relatively polydispersed polyester-based macroinitiator
in the copolymer. For example, when the block copolymer contain about 1420wt% of
63

polyester, a decrease of PDI of macroinitiator from 1.6 to a value of 1.3 for block
copolymer (Table 3- 3) was observed.
Table 3- 3 Results of ATRP of MMA and EMA using SPE-based macroinitiators
Polyester Mn (g / mol) PDI Block copolymer Conv.
b)
Mn (g / mol) PDI
(macro-
initiator)
a)
NMR GPC

[%] Theor. NMR GPC
AA-HD-1-A 1925 1900 1.60 PMMA-b-AA-HD-1-A-b-PMMA 50 3700 3500 4500 1.58
AA-HD-1-A 1925 1900 1.60 PMMA-b-AA-HD-1-A-b-PMMA 90 12500 12000 14000 1.27
AA-HD-1-C 2580 2600 1.70 PEMA-b-AA-HD-1-C-b-PEMA 85 20000 20000 21000 1.26
IPA-HD-1 1825 1800 1.65 PMMA-b-IPA-HD-1-b-PMMA 92 6400 6800 7000 1.60
PA-HD-1 1450 1400 1.60 PMMA-b-PA-HD-1-b-PMMA 80 5400 6000 6000 1.55
PA-HD-1 1450 1400 1.60 PEMA-b-PA-HD-1-b-PEMA 85 5700 6000 6500 1.58
AA-NPG-1 1725 1700 1.60 PMMA-b-AA-NPG-1-b-PMMA 85 7700 8000 8000 1.52
AA-NPG-1 1725 1700 1.60 PEMA-b-AA-NPG-1-b-PEMA 90 8000 7900 8500 1.50
AA-HD-2-A 1920 1900 1.60 PBA-b-AA-HD-2-A-b-PBA 70 7500 7000 8000 1.41
AA-HD-2-A 1920 1900 1.60 PEHA-b-AA-HD-2-A-b-PEHA 75 16900 16000 18000 1.36
AA-HD-2-A 1920 1900 1.60 PEHA-b-AA-HD-2-A-b-PEHA 40 3500 3000 3400 1.44
PEHA-b-AAHD- 3400 3000 1.44 PMMA-b-PEHA-b-AA-HD-2- 30 6400 7000 7900 1.79
2-A-b-PEHA

A-b-PEHA-b-PMMA
AA-HD-1-A 1925 1900 1.60 PMMA-b-AA-HD-1-A-b-PMMA 80 9900 9500 10900 1.30
AA-HD-1-A 1925 1900 1.60 PMMA-b-AA-HD-1-A-b-PMMA 25 2500 2400 3000 1.59
AA-HD-2-B 2280 2300 1.60 PEHA-b-AA-HD-2-B-b-PEHA 90 5000 5000 5500 1.54
AA-NPG-2 1720 1700 1.60 PEHA-b-AA-NPG-2-b-PEHA 90 6200 6500 7000 1.50
AA-NPG-2 1720 1700 1.60 PBA-b-AA-NPG-2-b-PBA 85 6000 6000 6800 1.52
PA-HD-2 1430 1400 1.60 PBA-b-PA-HD-2-b-PBA 85 5700 6200 6500 1.58
IPA-HD-2 1820 1800 1.65 PEA-b-IPA-HD-2-b-PEA 88 8000 8300 9000 1.60
PA-HD-2 1430 1400 1.60 PEA-b-PA-HD-2-b-PEA 80 5400 5800 6500 1.55
a) Macroinitiators used to polymerize the methacrylate monomer; b) Calculated from
gravimetrical data
64

In the bulk ATRP of acrylates the CuBr/PMDETA catalyst was stable and no
disproportionation occurred. The rate of polymerization was faster than CuBr/bpy
catalyst systems. This is because of the lower redox potential of Cu(I)/PMDETA
complex than Cu(I)/bpy complex.
Figure 3- 7 shows representative GPC chromatograms of starting macro-initiator
SPE1 (Table 3- 1, entry 2) (a), PMMA-b-SPE1-b-PMMA (Table 3- 3, entry 2) (b) and
PEMA-b-SPE1-b-PEMA (Table 3- 3, entry 3) tri-block copolymers, respectively. Figure
3- 8 shows representative GPC traces of starting (a) SPE2 macroinitiator (Table 3- 1,
entry 2), (b) PBA-b-SPE2-b-PBA (Table 3- 3, entry 9) and (c) poly(EHA)-b-SPE2-b-
poly(EHA) (PEHA-b-SPE2-b-PEHA, Table 3- 3, entry 10) tri-block copolymers,
respectively. In all the cases PDI of the tri-block copolymer was lower than that of the
macroinitiator. The symmetrical GPC chromatograms of block copolymers and the
shifting to high molecular side indicate efficient initiation of SPEs-based macroinitiators.
The efficacy of the synthesis of acrylate to methacrylate block copolymer was verified by
synthesizing penta-block copolymer of PMMA-b-PEHA-b-SPE2-b-PEHA-b-PMMA by
further initiation of PEHA-b-SPE2-b-PEHA. Figure 3- 9 shows the GPC chromatograms
of (a) PEHA-b-SPE2-b-PEHA (Table 3- 3, entry 11) and (b) PMMA-b-PEHA-b-SPE2-b-
PEHA-b-PMMA (Table 3- 3, entry 12). There is an increase of PDI (1.79) of the penta-
block copolymer in compare to PDI (1.44) of tri-block macroinitiator. This is attributed
to the slow initiation of triblock copolymer than the propagation of MMA. The GPC trace
of pentablock copolymer also shows tail at low elution volume suggesting possibility of
unreacted staring macroinitiator with dead chain ends.
65


Figure 3- 7 GPC traces of (a) SPE1, (b) PMMA-b-SPE1-b-PMMA and (c) PEMA-b-
SPE1-b-PEMA tri-block copolymers, respectively


Figure 3- 8 GPC traces of (a) SPE2 macroinitiator, (b) PBA-b-SPE2-b- PBA and (c)
PEHA-b-SPE2-b-PEHA tri-block copolymers, respectively.

12 14 16 18 20 22


I
n
t
e
n
s
i
t
y
b: Mn=13700
PDI=1.27
c: Mn=21200
PDI=1.26
a: Mn=1900
PDI=1.58
Elution Volume (ml)



12 14 16 18 20 22

I
n
t
e
n
s
i
t
y
c: Mn=17900
PDI=1.36
b: Mn=8000
PDI=1.41
a: Mn=1900
PDI=1.58
Elution Volume (ml)


66



Figure 3- 9 GPC traces of (a) PEHA-b-SPE2-b-PEHA tri-block and (b) PMMA-b-PEHA-
b-SPE2-b-PEHA-b-PMMA penta-block copolymers, respectively
3.6.4 Glass transition temperatures of different polyester-based copolymers
The T
g
s of the UPE and SPEs and their corresponding block copolymers were
determined by DSC analyses. Figure 3- 10 shows the DSC of the UPEs and their block
copolymers. The UPE (Table 3- 1, entry 2) shows T
g
at 19.3C. The tri-block
copolymers of UPE, i.e., PMMA-b-UPE1-b-PMMA (Table 3- 2, entry 11), PEHA-b-
UPE2-b-PEHA (Table 3- 2, entry 14), PEA-b-UPE2-b-PEA (Table 3- 2, entry 2) and
PBA-b-UPE2-b-PBA (Table 3- 2, entry 13) show T
g
s of 20, 65, 23.5 and 45.7C. On
the other hand, the pentablock-copolymer PMMA-b-PEHA-b-UPE2-b-PEHA-b-PMMA
(Table 3- 2, entry 15) shows a single (broad) T
g
at 58.73C

12 14 16 18 20 22

I
n
t
e
n
s
i
t
y
b: Mn=7900
PDI=1.79
a: Mn=3400
PDI=1.44
Elution Volume (mL)


67

-100 -50 0 50 100
f
e
d
c
b
a


(x 4)
(x 4)
H
e
a
t

F
l
o
w
,

E
x
o

U
p
Temperature (
o
C)

Figure 3- 10 The DSC thermograms of (a) PMMA-b-PEHA-b-UPE2-b- PEHA-b-PMMA,
(b) PMMA-b-UPE1-b-PMMA, (c) UPE, (d) PEA-b- UPE2-b-PEA, (e) PBA-b-UPE2-b-
PBA and (f) PEHA-b-UPE2-b-PEHA copoymers, respectively
Figure 3- 11 shows the DSC of the SPEs and their block copolymers. The SPE
(Table 3- 1, entry 2) shows T
g
at 21C which is close to the T
g
of UPE. The tri-block
copolymers PMMA-b-SPE1-b-PMMA (Table 3- 3 entry 13), PMMA-b-SPE1-b-PMMA
(Table 3- 3 entry 14) and PEHA-b-SPE2-b-PEHA (Table 3- 3 entry 11) show T
g
s at 79,
20 and 38.13C and the pentablock-copolymer PMMA-b-PEHA-b-SPE2-b-PEHA-b-
PMMA shows a (broad) T
g
at 52C.
68

-80 -60 -40 -20 0 20 40 60 80 100 120
(x 16)
(x 16)
(x 8)
(x 8)
(x 8)
e
d
c
b
a


H
e
a
t

F
l
o
w
,

E
x
o

U
p
Temp(
o
C)
(1st heating)
(2nd heating)

Figure 3- 11 The DSC thermograms of (a) SPE, (b) PEHA-b-SPE2-b- PEHA, (c)
PMMA-b-SPE1-b-PMMA, (d) PMMA-b-SPE1-b-PMMA and (e) PMMA-b-PEHA-b-
SPE2-b-PEHA-b-PMMA copolymers, respectively.
In all the block copolymers only one T
g
was observed which was in between the
glass transition temperature of polyesters and (meth)acrylates. The measured T
g
values
are close to the T
g
determined by Fox equation.
133
The appearance of single T
g
of all
block copolymers can be readily explained by the miscibility of polyester with respective
(meth)acrylate blocks. The miscibility arises due to the (i) formation of block copolymer
and (ii) the ester functional group present in (meth)acrylate side chains.
In contrast to UPE the SPE shows melting temperature (T
m
) at 43C
(H=48.38Jg
1
) due to crystalline nature of the polyester. The thermograms of the tri-
block copolymers PMMA-b-SPE1-b-PMMA (T
m
=70.3C, H=2.73Jg
1
) (Table 3- 3
69

entry 13), PMMA-b-SPE1-b-PMMA (T
m
=42.75C, H=31.06Jg
1
) (Table 3- 3 entry
14), PEHA-b-SPE2-b-PEHA (T
m
=36.4C, H=23.6Jg
1
) (Table 3- 3 entry 11) after
first heating cycle (Figure 3- 11) shows a melting temperature specific to polyester block.
After second heating cycle T
m
s of the polyesters were detected for tri-block copolymers
PMMA-b-SPE1-b-PMMA (T
m
=43.49C) (Table 3- 3 entry 14) and PEHA-b-SPE2-b-
PEHA (T
m
=35.13C) (Table 3- 3 entry 11) with a weaker melting enthalpy (Figure 3-
10). This may be due to the disruption of the crystalline structure of the polyester during
the first heating run and did not grow back to the similar extent during the short heating
time of the second run. This suggests that the greater the amount of PMMA the more
difficult it is for the polyester to self-organize upon cooling.
The block copolymers containing more than 20wt% of polyester middle block
show T
m
some what lower than the T
m
of polyester. This result thus suggests that the
block copolymers still are flexible and shows crystallinity. Due to combination of
flexibility and crystallinity the polyester based acrylic copolymers might be useful as
high strength and flexible coating material.
3.6.5 Network formation from unsaturated polyester-based block copolymers
The network formation and the disappearance of double bond in the UPE-based
block copolymers were monitored by photo DSC. Figure 3- 12 shows the heat flow
versus time plots for UPE and three PEHA-b-UPE-b-PEHA copolymers of different
molecular weights. The heat of reaction for the photo polymerization of UPE (Figure 3-
12, plot a) was 358.4Jg
1
. The heat of reaction decreased from 254.3 to 206Jg
1
with
increased molecular weight of the block copolymers from 6 000 to 10 000, respectively.
The method of determining photo polymerization of UPE2-block-polyacrylate block
70

copolymers is in accordance to a study by Tryson and Shultz.
134
The exothermic reaction
showed the significant changed at the early stage of exposure time, which indicates the
polymerization of UPE2-block-polyacrylate, and then it gradually decrease due to
termination reaction or by the reduction of double bond in the block copolymers.

Figure 3- 12 Heat flow versus time plot of a series of UV-curable polyesters: (a) neat
UPE and (b), (c), (d) are three different PEHA-b-UPE-b-PEHA copolymers of molecular
weights 5550, 7400 and 9600, respectively.
3.7 Conclusions
In conclusions, the low cost synthesis of series of novel SPE- and UPEs-based
block copolymers of (meth)acrylates were accomplished by the combination of
condensation polymerization and ATRP. The polymerizations were well controlled and
the main chain double bonds in the unsaturated polyester backbones remained almost

0.5 1.0 1.5 2.0 2.5
b
c
d
a


H
e
a
t

F
l
o
w
,

E
x
o

U
p
Time(Min)
71

unaffected during polymerization. Because of network formation upon irradiation the
UPE-based block copolymer could be suitable candidate for UV curable solvent resistant
coating material with superior weather properties.

72

CHAPTER IV

THERMAL CURABLE POLYURETHANE-UREA COATING BASED ON
POLYESTER POLYOLS

4.1 Abstract
Polyurethane-urea (PUU) coatings were formulated using Partially Blocked HDI
isocyanurate (PBH), isophorone diamine (IPDA), and polyester polyol. The partially
blocked isocyanate (HBP) was prepared from the reaction of the HDI isocyanurate with
2-butanone oxime as a blocking agent. The reaction of the amine/alcohol with the
isocyanate was reduced due to the usage of the PBH. As a comparison, the polyurethane
coatings (PU) without adding IPDA were also prepared. The thermo-mechanical
properties of the PUU and PU coating were investigated by tensile test and DMTA. The
glass transition temperature (T
g
) and crosslink density of the coatings were derived from
the tan and storage moduli (E), respectively. It was found that the PUU coating
exhibited higher crosslink density, Tg, tensile modulus and tensile strength value than the
corresponding PU coating.
73

4.2 Introduction
Polyurethane resins are typically prepared from the reaction of the polyisocyanate
with polyol, while polyurea resins are typically prepared from the reaction of the
polyisocyanate with polyamine. The preparation schemes of urethane and urea are shown
in Figure 4- 1. Polyurethane resins have wide applications in coatings such as wood,
plastic, automotive, industrial coatings
77
, because polyurethane coatings show superior
chemical and solvent resistance, flexibility, superior adhesion, and abrasion and corrosion
resistance
34
. The properties of the polyurethane coating can be can be easily tailored by
varying the polyols and polyisocyanate
135
. The most common polyols are polyester
polyols and followed by polyether polyols. Isocyanate can be aromatic or aliphatic.
Aromatic isocyanates react faster than aliphatic isocyanates and are less expensive.
Aliphatic isocyanates have better color retention and exterior durability
77
.

Figure 4- 1 General synthetic scheme for (a) urethane, (b) urea
Compared with polyurethane coating, polyurea coating has less wide
applications due to two major drawbacks. One is the faster curing of the polyurea, the
reaction of the isocyanate and amine could be cured within seconds, which makes it good
for only two-component spray coating application, but limits its wide application for

R NCO R' OH
R
N OR'
H
O
R NCO R' NH
2 R
N N
H
O
R'
H
a.
b.
74

other coatings
136,137
. Another drawback is that polyamine starting raw material for
polyurea is very limited, and usually polyamine is based on the polyether amine.
Several strategies have been reported to decrease the reaction of the amine and
isocyanate. Such as using hindered amine
138
, blocked amine
138
and blocked
isocyanate
139,140,141,142,45
reduce the reactivity of the amine towards isocyanate. Hindered
amine could be prepared from the reaction of the primary amine with dialkyl maleates via
the Michael addition. Blocked amine could be prepared from the reaction of the primary
amine with carbonyl compound via the imine formation route
138
. Blocked isocyanate
could be prepared from the reaction of the isocyanate with an active hydrogen compound.
Upon heating, the blocked isocyanate decomposes and releases the free isocyanate which
reacts with coreactant to form polyurethane or polyurea, respectively
44
. The overall
reaction is illustrated in Figure 4- 2. The polyurea coating could also be formed based on
moisture curing route. In this case, polyisocyanate reacts with moisture to form free
amine. The in-situ generated amine reacts immediately with polyisocyanate forming urea
linkage.
138, 143


Figure 4- 2 General synthetic scheme for preparation of polyurea and polyurethane from
the blocked isocyanate

R NCO B H R N C B
O
H
R NCO B H
R'OH / R'NH
2
Urethane / Urea
B-H : Blocking agent
75

One of main advantages of polyester over polyether is its more varieties.
Industrial polyether is generally limited in monomer composition to propylene oxide,
ethylene oxide, butylene oxide and tetrahydrofuran. Industrial polyester is the
condensation product of acids and alcohols. The variety of the combination of acids and
alcohols adds to the potential versatility of polyester
144
. It has been reported that the
amine terminated polyester has been prepared
145
, but the reaction step is complex, which
makes it impossible for large-scale production and coating applications. And also, the
amine terminated polyester is unstable. The aminolysis of the ester backbone is easy to
take place due to the existence of the terminated amine function group. This limits the
preparation of the polyurea from the reaction of the polyisocyanate with amine
terminated polyester.
In this article, partially blocked isocyanate was prepared to decrease the reaction
of the alchol and isocyanate. The mixture of the polyester polyol, partially blocked
isocyanate and isophorone diamine (IPDA) were chosen as the starting materials to
prepare polyurethane-urea (PUU) coatings. Such polyurethane-urea (PUU) coatings were
expected to have a longer pot life than conventional 2K polyurea or polyurethane coating,
a better mechanical property than polyurethane coating due to the existence of the extra
urea function group, and a better abrasion resistance and chemical resistance property
than polyether polyurea coating due to the existence of the ester function group. As a
comparison, the polyurethane coatings (PU) without adding IPDA were also prepared.
The mechanical properties of the PUU and PU coating were investigated by using tensile
test and DMTA. The glass transition temperature (T
g
) and crosslink density of the
coatings were derived from the tan and storage moduli (E), respectively.
76

4.3 Materials
Adipic acid (AA), isophthalic acid (IPA), 1,4 butanediol (BD), 1,5-pentanediol
(PD), 1,6 hexane diol (HD), p-xylene, dibutyl tin oxide (DBTO), dibutyltin dilaurate,
isophorone diamine (IPDA) tetrahydrofuran (THF), 2-butanone oxime (BKO) all Aldrich
products were used as received, HDI isocyanurate (3HDI) (Desmodur N-3300, NCO
content 21%) was provided by Bayer Corp. The chemical structures of the monomers for
preparation of the polyester are shown in Figure 4- 3.

Figure 4- 3 Structures of the monomers for preparation of polyester polyols
4.4 Instrumentation and characterization
Fourier Transform Infrared Spectroscopy was obtained on a Nicolet 380 FTIR
instrument (Thermo Electron Corp.). The NMR spectra were taken in a Varian Mercury
300 MHz spectrophotometer. Gel permeation chromatography measurements were
performed on a Waters GPC instrument equipped with a series of six Styragel columns
(HR 0.5, HR 1, HR 3, HR 4, HR 5 and HR 6) calibrated with narrow-MWD polystyrene

COOH
COOH
OH
HO
HO OH
HO
OH
HOOC
COOH
Isophthalic Acid (IPA)
AdipicAcid (AA)
1,6-Hexanediol (HD)
1,5-Pentanediol (PD)
1,4-Butanediol (BD)
77

standards. Tetrahydrofuran was used as the mobile phase with a flow rate of 1.0 mL/min.
A refractive index (RI) detector (Optilab, Wyatt Technology), and a dual-ultraviolet
absorbance detector (Waters 2487), and a laser light scattering detector (Minidawn,
Wyatt Technology) were used to obtain number average molecular weight Mn, weight
average molecular weight Mw and polydispersity index (PDI). Glass transition and
melting temperatures for all samples were measured on a Q1000 differential scanning
calorimeter (DSC) from TA Instruments at a heating rate of 10C/min. The experiments
were run under nitrogen atmosphere.
Viscoelastic properties of the cross-linked films were obtained with a Perkin
Elmer Pyris Dyamond Dynamic Mechanical Thermal Analyzer (DMTA) with a
frequency of 1 Hz and a heating rate of 3
0
C/min over a range of -50 to 120
0
C. The gap
distance was set up at 4 mm for rectangular specimens (length 10 mm, width 8-10 mm
and thickness 0.09-0.11 mm). The crosslinking density was determined from the rubbery
plateau in the storage modulus vs. temperature plot. Glass transition temperature (T
g
) of
the crosslinked polyester-urethane-ureas were determined from the tan vs temperature
plots.
The tensile properties were obtained by an Instron Universal Tester model 1000.
The dimensions of the films for tensile testing were 0.09-0.11 mm in thickness, 6.5 mm
wide and an initial length of 25 mm. A crosshead speed of 10 mm/min was applied. All
the testing was carried out at room temperature. The modulus, tensile stress, and
elongation at break were measured. The stress and the strain were calculated using the
following equations:
t w
F
A
F

(4-1)
78


o
L
L
(4-2)
In which, is the stress, means the strain, F is the load, w is the width, t is the
thickness, L is the change in length of the gauge, and L
o
is the initial gauge length. So,
using the given load and elongation data, stress vs. strain plots was constructed.
Pencil hardness (ASTM D 3363-74), cross-hatch adhesion (ASTM D 3359-87),
pull-off adhesion (ASTM D 4541-85), impact and reverse impact resistance (ASTM D
2784-94) were performed according to ASTM standards.
4.5 Synthesis
In this synthesis part, four different kinds of polyester polyols were synthesized
by the direct polymerization of diacids and diols. The PBH was synthesized by the
reaction of HDI isocyanurate with blocking agent.
4.5.1 Synthesis of polyester polyol
To synthesize hydroxyl terminated polyester, excess diol was used. The molar
ratio of diol to diacid is 3:2. A representative example of synthesis of polyester polyol is
as follows. For synthesis of AA-BD polyester diol, in a 500 ml four-neck round bottom
flask which is equipped with a mechanical stirrer, a gas inlet, a temperature controller, a
Dean-Stark trap and a condenser, adipic acid (131.53 gm, 0.90 mol), 1,4 butanediol (122
gm, 1.35 mol) was added under argon atmosphere to minimize oxidative degradation. To
accelerate the reaction, DBTO (0.4 wt %, 1.01 g), a transesterification catalyst, was used.
Then xylene (3 wt %, 7.61 g) was also added to remove water from the resin as a form of
azeotropic mixture. In order to minimize the glycol loss by evaporation the reaction
79

temperature was carefully controlled using a temperature controller and a thermocouple.
The mixture was heated to 210
0
C. The final temperature was held until the resin had an
acid number measured by titration less than or equal to 10 mg KOH/g resin (ASTM D
1639-90). The reaction was completed after 5 hrs and final acid number was 4.9 mg
KOH/g resin.
Other polyesters, such as AA-PD and AA-HD were synthesized using the same
procedure. For AAIPA-HD polyester synthesis, the molar ratio of diol to diacid is 3:2
while keeping the ratio of AA to IPA is 1:1. The properties of the polyester polyols are
shown in Table 4- 1.
Table 4- 1 Physical property of the synthesized polyester polyols
*Polyester in methyl ethyl ketone (MEK) solution with polyester concentration of 70 wt %
4.5.2 Synthesis of partially blocked HDI isocyanurate (PBH)
For the synthesis of PBH, in a three neck round bottom flask, HDI isocyanurate
(3HDI) (80 g, 0.40 mol NCO) was dissolved in dry THF (80 ml) and cooled to 0
0
C.
dibutyltin dilaurate (0.04 g) was added into it. Next, 2-butanone oxime (29.04 g,0.33 mol)
blocking agent was added drop wise with constant stirring under nitrogen atmosphere and
kept for 2 h at 0
0
C. The mixture was then allowed to stir for overnight at room
temperature. THF was removed under vacuum and the product was characterized by IR
and NMR. The free NCO content is 2.6 wt% and blocked NCO content was 12.9 wt%.
Polyester Acid # Hydroxyl # M
n
PDI
Viscosity
(mP
a
s) T
g
(
0
C) T
m
(
0
C)
AA-BD 4.9 155.6 1125 1.34 67.19 -20.4 38.8
AA-PD 6.5 222.1 1086 1.50 52.79 -5.0 30.0
AA-HD 6.1 247.2 1101 1.46 33.59 -3.0 41.0
AAIPA-HD 6.3 176.5 1150 1.27 33.49 -55.8 3.1
80

The product partially blocked isocyanurate (PBH) was characterized by IR and NMR
spectroscopy.
4.6 Coating formulation
For preparation of the polyester polyurethane (PU) coatings, polyesters were
diluted in methyl ethyl ketone (60 wt% of polyester) and then mixed with the polymer of
hexane 1,6 diisocyanate (HDI) isocyanurate. The mole ratio of isocyanate group to
hydroxyl group is kept constant at 1.1/1.0). The flow aid agent Tego wet 270 (0.2 wt%,
based on the total solid) was added into the mixture. For preparation of the polyester
polyurethane-urea coatings (PUU), polyesters were diluted in methyl ethyl ketone (60 wt%
of polyester) and then mixed with the isophorone diamine (IPDA) and partially blocked
hexane 1,6 diisocyanate (HDI) isocyanurate (PBH). The mole ratio of isocyanate group to
hydroxyl and amine group is kept constant at NCO: OH: NH
2
= 1.1: 0.7: 0.3. Then the
flow aid agent Tego wet 270 (0.2 wt%, based on the total solid) was added into the
coating formulations to adjust the surface tension and obtain crater-free films. The films
were cast on the aluminum panels with the thickness of 6 mil by a drawbar for the
general coating testing. The films were cured at 120
0
C for 1h. For mechanical and tensile
properties the films were casted on a glass panel with a thickness of 8 mil. The cured
films were stored for 3 days under ambient atmospheric conditions before testing. Actual
composition for the formulation of polyurethane (PU) and polyurethane-urea coatings
(PUU) coatings is given in Table 4- 2.



81

Table 4- 2 Formulation of polyurethane-urea (PUU) and polyurethane (PU) coatings
Sample
Polyester IPDA Crosslinker*
MEK
(gm)
Tego
270
(gm) Wt. (g)
OH
(mmol) Wt. (g)
NH
2
(mmol) Wt. (g)
NCO**
(mmol)
AA-BD-PUU 10.00 27.79 1.01 11.90 11.88 43.66 6.67 0.046
AA-PD-PUU 10.00 39.64 1.45 17.00 16.96 62.30 6.67 0.057
AA-HD-PUU 10.00 44.11 1.60 18.85 18.85 69.26 6.67 0.061
AAIPA-HD-PUU 10.00 31.52 1.15 13.55 13.49 49.58 6.67 0.049
AA-BD-PU 10.00 27.79 5.14 30.57 6.67 0.030
AA-PD-PU 10.00 39.64 7.33 43.60 6.67 0.035
AA-HD-PU 10.00 44.11 8.16 48.52 6.67 0.036
AAIPA-HD-PU 10.00 31.52 5.83 34.67 6.67 0.032
*The crosslinker was used modified HDI isocyanurate (PBH) for PUU coating, and HDI
isocyanurate for PU coatings
** For PUU coating, total NCO content was used including the blocked NCO
4.7 Results
The objective of this study was to prepare polyester based polyurethane-urea
hybrid coatings. Isophorone diamine (IPDA) was selected to work as a chain extender
and also provide urea function group. Partially blocked HDI isocyanurate (PBH) was
chosen with two functionalities: One function is to slow down the reaction of the
isocyanate with polyester polyol and increase the pot life, since the isocyanate function
group is blocked. Another function is to reduce the loss of the IPDA at high curing
temperature (120
o
C), since the amine group in the IPDA reacts with the free isocyanate
group in the PBH during the mixing at room temperature, making the IPDA less volatile.
The diol and diacid starting materials were varied to change the properties of the
polyester polyol, thus the properties of the polyureane-urea coating (PUU). The
polyurethane coatings (PU) without adding IPDA were also prepared to compare with the
PUU coatings.
82

4.7.1 Preparation of partially blocked HDI isocyanurate (PBH)
The preparation method of partially blocked HDI isocyanurate (PBH) was
illustrated in Figure 4- 4a. The reaction of the HDI isocyanurate with blocking agent 2-
butanone oxime (BKO) was carried out at 0
0
C followed by at room temperature. 83.3 %
of the NCO was reacted with 2-butanone oxime (BKO) to form the blocked NCO, and
16.7 % free NCO was left.


Figure 4- 4 Reaction strategy for preparation of coatings, (a) polyester-urethane-urea
(PUU) coatings, (b) polyester-urethane (PU) coatings

N
HO
HB =
N N
N O O
O
CH
2
NCO
6
CH
2 NCO
CH
2 OCN
6 6
N N
N O O
O
CH
2
NH
6
CH
2 NH
CH
2 HN
6 6
O
B
O
B
O
B
NCO
0.5 0.5
2.5 HB
PBH
NH
2
NH
2
HO PE OH
Polyester-urethane-urea (PUU) Coating
HO PE OH
= Polyester Polyol
b.
N N
N O O
O
CH
2
NCO
6
CH
2 NCO
CH
2 OCN
6 6
HO PE OH
Polyester-urethane (PU) Coating
a.
83

The formation of the blocked NCO and the existence of the free NCO were
confirmed by the FTIR and NMR. The FTIR analysis performed in HDI isocyanurate
(3HDI) and partially blocked HDI isocyanurate (PBH) were shown in Figure 4- 5.
Characteristic band of the free isocyanate group in 3HDI was obtained in the 2247 cm
-1

region. In the PBH, the FTIR shows less intense band in the 2247 cm
-1
region, which
means that there is still free isocyanate left in PBH. The new bands in the range of 3390
cm
-1
and 1730 cm
-1
regions are attributed to the N-H bond stretching with urethane and
C=O non-bonded urethane stretching, which indicates the formation of the urethane in
the PBH.

Figure 4- 5 IR spectrum of partially blocked HDI isocyanurate (PBH)
1
H NMR and
13
C NMR analysis performed in partially blocked HDI isocyanurate
(PBH) are shown in Figure 4- 6. The
1
H NMR spectra in Figure 4- 6a show one
resonance at 7.20 ppm indicating the presence of proton from urethane group. The
13
C
84

NMR spectra in Figure 4- 6b shows one resonance at 122.20 ppm indicating the
presence of free isocyanate (-N=C=O) function group.

Figure 4- 6 NMR of partially blocked HDI isocyanurate (PBH), (a)
1
H NMR and (b)
13
C
NMR
4.7.2 Tensile properties
The tensile strength, elongation at break, and tensile modulus of PUU and PU
coatings synthesized from different polyester polyols are shown in Figure 4- 7, and
summarized in Table 4- 3. For both PUU and PU coatings, the tensile strength and
modulus was increased in the order of the systems containing the diol of 1,4-butanediol
(AA-BD); 1,5-pentanediol (AA-PD); and 1,6-hexanediol (AA-HD). And the strength and
modulus was further increased with the incorporation of the aromatic diacid isophthalic
acid (IPA) into the system. The elongation at break is in the range of 100 ~ 150 % for the
all the PUU coating systems. The elongation at break is in the range of 20 ~ 50% for AA-
BD, AA-PD, and AA-HD based PU coating, and 150% for AA-HD based PU coating. As
a comparison of the PUU coating with PU coating, it was found that the tensile modulus
of PUU coating is around 2 ~ 3 times higher than those of the PU coatings. The tensile
a. b
.
85

strength of the PUU coating is around 3 ~ 6 times higher than those of the PU coatings.
The elongation at break of the PUU coating is around 3 ~ 5 times higher than those of the
PU coatings except the AAIPA-HD based coating. In that case, AAIPA-HD PUU coating
showed slightly lower elongation at break than AAIPA-HD PU coating.


Figure 4- 7 Tensile properties of PUU and PU coatings, (a) tensile strength, (b) tensile
modulus, (c) elongation at break





a. b
.
c.
86

Table 4- 3 Tensile Properties of of polyurethane-urea (PUU) and polyurethane (PU)
coatings
Samples Modulus (MPa) Tensile stress (MPa) Elongation at break (%)
AA-BD-PUU 9.28 0.43 5.87 1.18 118.73 15.31
AA-PD-PUU 12.72 2.19 9.38 1.04 150.52 11.85
AA-HD-PUU 13.64 2.90 11.33 3.51 148.92 26.02
AAIPA-HD-PUU 55.58 15.41 14.30 0.95 95.48 7.17
AA-BD-PU 4.46 0.61 0.95 0.48 27.61 14.98
AA-PD-PU 7.97 0.52 1.98 0.78 28.63 10.30
AA-HD-PU 8.34 0.74 2.87 1.30 44.00 19.79
AAIPA-HD-PU 15.18 1.17 6.48 4.71 150.16 59.82

4.7.3 Viscoelastic properties
The viscoelastic properties of the PUU and PU coating films were investigated
using DMTA. The storage modulus E and the tan transition of PUU and PU coatings
synthesized from different polyester polyols are shown in Figure 4- 8 and Figure 4- 9.
The storage modulus (E) remained almost constant as the temperature was increased up
to the glass transition and started to decrease during the transition. The decrease reached
a minimum value and then slightly increased with temperature forming a rubbery plateau.
This changing tendency follows the general rule described as equation below
146

E = 3
e
RT (T >> Tg) (4-3)
where
e
is the number of moles of elastically effective network chains per cubic
meter of film and E is tensile storage modulus. This relationship is effective when
T >>Tg, and for low crosslink density elastomers. For the highly crosslinked system, it
can only be used to evaluate the relative density of crosslinking. Crosslink density was
calculated by this equation with the E at corresponding temperature T (T > Tg + 50
o
C).
The minimum of storage modulus, E(min), was recorded as the minimum value in
rubbery plateau. The Tg was obtained from the maximum of the -transition.
87

The storage modulus Eof PUU and PU coatings synthesized from different
polyester polyols are shown in Figure 4- 8. The E (min) and the crosslink density (
e
) of
the PUU and PU coatings were independent of the type of the polyester polyols. In
comparison with the PU coatings, the PUU coatings exhbited higher E(min) and the
crosslink density (
e
) than the corresponding PU coatings. This is due to the incorporation
of the IPDA chain extender in PUU coatings. The incorporation of the IPDA could
contribute the formation of urea and the increase of crosslink density, leading to the
increase of the storage modulus.

Figure 4- 8 Modulus (E) as a function of temperature of polyurethane-urea (PUU) and
polyurethane (PU) coatings based on (a) AA-BD, (b) AA-PD, (c) AA-HD, (d) AAIPA-
HD

-60 -40 -20 0 20 40 60 80 100 120
10
5
10
6
10
7
10
8
10
9


E
'
(
M
P
a
)
Temperature (
o
C)
AABD-PU
AABD-PUU
a.
-60 -40 -20 0 20 40 60 80 100 120
10
6
10
7
10
8


E
'
(
M
P
a
)
Temperature (
o
C)
AAPD-PU
AAPD-PUU
-60 -40 -20 0 20 40 60 80 100 120
10
6
10
7
10
8


E
'
(
M
P
a
)
Temperature (
o
C)
AAHD-PU
AAHD-PUU
c.
-60 -40 -20 0 20 40 60 80 100 120
10
5
10
6
10
7
10
8


E
'
(
M
P
a
)
Temperature (
o
C)
AAIPAHD-PU
AAIPAHD-PUU d.
88

The tan of PUU and PU coatings synthesized from different polyester polyols
are shown in Figure 4- 9. The breath and maximum of tan of the PUU and PU coatings
were independent of the type of the polyester polyols for AA-BD, AA-PD, and AA-HD.
The breadth of tan and maximum of tan was decreased with incorporation of the
aromatic diacid isophthalic acid (IPA) into the system. As comparison of the PU coatings,
PUU coatings showed higher values in the breadth of tan and lower values in maximum
of tan, this indicated that the incorporation of the IPDA increased the heterogeneity of
cured coatings.

Figure 4- 9 Tan as a function of temperature of polyurethane-urea (PUU) and
polyurethane (PU) coatings based on (a) AA-BD, (b) AA-PD, (c) AA-HD, (d) AAIPA-
HD

-60 -40 -20 0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6


T
a
n

D
e
l
t
a
Temperature (
o
C)
AAIPAHD-PU
AAIPAHD-PUU
d.
-60 -40 -20 0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4


T
a
n

D
e
l
t
a
Temperature (
o
C)
AABD-PU
AABD-PUU
a.
-60 -40 -20 0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0


T
a
n

D
e
l
t
a
Temperature (
o
C)
AAPD-PU
AAPD-PUU
b.
-60 -40 -20 0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0


T
a
n

D
e
l
t
a
Temperature (
o
C)
AAHD-PU
AAHD-PUU
c.
89

The Tg, minimum elastic modulus (E), crosslink density (
e
), breadth of tan
transition, and maximum of tan transition of PUU and PU coatings synthesized from
different polyester polyols are summarized in Table 4- 4.
Table 4- 4 Viscoelastic properties of polyurethane-urea (PUU) and polyurethane (PU)
coatings
Sample
T for
E'
min
(MPa)

e

(mol/m
3
)
Tg
Tan
Breadth
(
o
C)
Max.
E'
min
(
o
C) (
o
C) Tan
AA-BD-PUU 66.95 3.21 378.53 -9.14 46.91 0.62
AA-PD-PUU 92.94 1.84 201.62 32.60 43.43 0.71
AA-HD-PUU 79.44 0.92 104.61 42.19 54.62 0.62
AAIPA-HD-PUU 103.24 1.45 154.13 15.73 36.71 1.03
AA-BD-PU 26.44 0.06 8.56 -9.54 20.28 1.29
AA-PD-PU 26.92 0.89 119.18 1.73 23.12 0.98
AA-HD-PU 30.03 0.78 103.15 2.53 31.26 0.93
AAIPA-HD-PU 49.55 0.34 42.24 -1.30 22.19 1.56

4.7.4 General coating properties
A summary of the PUU and PU coating properties is found in Table 4- 5. After
thermal curing, several film properties were evaluated: pencil hardness, cross-hatch
adhesion, gloss, and impact resistance. The type of the polyester polyol and the
incorporation of the IPDA did not affect pencil hardness, impact resistance, and cross-
hatch adhesion of the coatings.






90

Table 4- 5 Coating properties of polyurethane-urea (PUU) and polyurethane (PU)
coatings

Sample

Pencil
Hardness
Cross-
hatch
adhesion

Gloss

Gloss

Impact
Reverse
Impact
20 60 (lb/inch) (lb/inch)
AA-BD-PUU 5H 5B 114.10 127.40 >40 >40
AA-PD-PUU 5H 5B 118.53 142.58 >40 >40
AA-HD-PUU 5H 5B 123.62 136.08 >40 >40
AAIPA-HD-
PUU
5H 5B 118.26 140.78 >40 >40
AA-BD-PU 5H 5B 93.76 123.22 >40 >40
AA-PD-PU 5H 5B 118.98 130.53 >40 >40
AA-HD-PU 5H 5B 119.50 132.60 >40 >40
AAIPA-HD-PU 5H 5B 123.25 137.42 >40 >40
4.8 Discussion
Polyester polyurethane-urea (PUU) coating crosslinking mechanism was
illustrated in Figure 4- 10. During the mixing step, half of the amine group in isophorone
diamine (IPDA) reacted with the free isocyanate function group in the partially blocked
isocyanurate (HBP), leading to the formation the urea. This step could not induce the
occurrence of the gelation although the viscosity of the mixture was increased since there
are no multi-functional groups involved in this reaction. On another hand, this step could
hold the isophorone diamine (IPDA) into the system, minimizing its loss in the following
heating step. During the heating step, the blocking agent 2-butanone oxime was released
and the free isocyanate was formed, such free isocyanate first reacted with the IPDA then
reacted with the polyester polyols. Thus crosslinked polyester polyurethane-urea coating
was formed. For the preparation of the polyester polyurethane coating as illustrated in
Figure 4- 4-b, during the mixing step, the free isocyanate function group reacted with the
hydroxyl group in the polyester polyol to form the polyurethane. This reaction could
induce the occurrence of the gelation since three-functional isocyanate group was
91

involved during this step. During the heating step, the reaction of the isocyanate with the
polyol was accelerated and crosslinked polyurethane (PU) coating was formed. As
comparison of the PUU coating with PU coating in terms of the formulation step at room
temperature and the following crosslinking step at relative high temperature, it was found
that the PUU coatings showed longer pot-life than corresponding PU coatings, which
makes PUU coating easier to handle during the formulation step.

Figure 4- 10 Reaction mechanism for preparation of the polyester polyurethane-urea
coatings
As a comparison of the PUU coating with PU coating, it was found that the tensile
modulus and tensile strength of PUU coating showed higher values than those of the
corresponding PU coatings. This could be explained that the addition the IPDA leads to
formation of the urea unit, increase in physical interaction forces from the hydrogen
bonding among urea groups and increase in the hard segments content of the crosslinked
films. The elongation at break of the PUU coating also showed higher values than those
of the PU coatings except the AAIPA-HD based coating. In that case, AAIPA-HD PUU
coating showed slightly lower elongation at break than AAIPA-HD PU coating. Such

N N
N O O
O
CH2
NH
6
CH2 NH
CH2 HN
6 6
O
B
O
B
O
B
NCO
0.5 0.5
PBH
NH
2
NH2
HO PE OH
Step 1. Mixing at RT
N N
N O O
O
CH2
NH
6
CH2 NH
CH2 HN
6 6
O
B
O
B
O
B
0.5
NH
O
NH2
N
H
0.5
Step 2.1. Deblocking at 120
o
C
N N
N O O
O
CH2
NCO
6
CH2 NCO
CH2 OCN
6 6
0.5
NH
O
NH2
N
H
0.5
N
HO
HB =
HO PE OH = Polyester Polyol
HB
OH PE HO
Step2.2. Crosslinking at 120
o
C
Polyester-urethane-urea (PUU) Coating
92

reduction in elongation for PUU coating could be explained that the incorporation of the
rigid aromatic unit restrict the polymer movement upon stretching
147
.
Compared with the PU coating, PUU coating with the incorporation of the IPDA
showed two major trends in the dynamic mechanical analysis. One corresponded to
broadening of the transition region and the other represented the shift of the maximum
tan value toward lower numbers and higher temperatures. The breadth of a transition
region is closely related to the degree of heterogeneity
125,148
. As given in Table 4- 4, tan
transition breadths was increased with the incorporation of IPDA, which suggested that
the existence of the IPDA has major impact on the heterogeneity, and the incorporation
of the IPDA cause the increase of heterogeneity of the systems. The crosslink density has
a direct impact on the tan such that it reduces long range segmental motion required for
viscous flow behavior
149
. As a result, the maximum tan can be used to measure the
extent of cure. The maximum tan in the tan curve decreases as the incorporation of
the IPDA. This indicates that the crosslink density of the PUU coating increases with the
incorporation of the IPDA. The maximum tan of PUU coating is lower than that of the
corresponding PU coating. This is another evidence to show that the PUU coating has a
higher crosslink density, and higher tensile and storage modulus. The Tg was obtained as
the maximum of tan . It was found the Tg increased with the incorporation of the IPDA,
and the Tg of PUU coating is higher than that of corresponding PU coating. An increase
in Tg corresponded to a decrease in mobility in the polymer. The extra formation of the
urea crosslinking networks in the PUU coating system would hinder the movement of the
polymer chains, resulting in the increase of the Tg
150
. It indicates that with incorporation
of the IPDA, the crosslink density of PUU coating enhanced, leading to the increase of
93

Tg of the coating. The Tg of PUU coating is higher than that of the PU coating. This can
be attributed to the additional physical crosslink density formation via the hydrogen
bonds between the urea groups in the PUU coating.
4.9 Conclusions
Thermal curable long pot life 2K polyester based polyurethane-urea (PUU)
coating was successfully prepared. During the formulation, four different polyester
polyols were chosen as the binders, isophorone diamine (IPDA) was chosen as the chain
extender and also as the reactant for the formation of urea units, and the partially blocked
HDI isocyanurate (PBH) was chosen as crosslinker to increase pot life and reduce the
loss the IPDA. As a comparison, the polyurethane coatings (PU) without adding IPDA
were also prepared. With the incorporation of the IPDA, the tensile modulus and tensile
strength of PUU coating showed higher values than those of the corresponding PU
coatings due to the formation of the urea unit and extra physical interaction forces from
the hydrogen bonding among urea groups. With the incorporation of the IPDA, PUU
coating showed higher value than the corresponding PU coating in terms of crosslink
density, Tg, and tan transition breadth.

94

CHAPTER V

PREPARATION OF THE THERMAL CURABLE NON-ISOCYANATE
POLYURETHANE COATINGS

5.1 Abstract
Non-isocyanate polyurethane coatings were prepared by the thermo-curing of the
polyamine and cyclic carbonate terminated polyester. Cyclic carbonate terminated
polyester was synthesized from the reaction of the carbon dioxide and epoxidized
polyester which was prepared from the polyester polyol with the epichlorohydrin under
the catalyst. The properties of the epoxidized and cyclic carbonate terminated polyester
were characterized by Brookfield viscometer, NMR and FT-IR. The cyclic carbonate
terminated polyester could react with polyamine to give non-isocyanate polyurethane
networks.
5.2 Introduction
Polyurethanes have been an important class of resins for organic coatings because
they have toughness, excellent wear and tear properties.
151
And polyurethanes are
usually synthesized through the polycondensation reaction between diisocyanate and
95

diol.
152
This is less desirable because the diisocyanate is highly hazardous, and the
phosgene which is the raw material of isocyanate is instable and toxic. It was known that
the carbamate group can be synthesized by the reaction of the primary amine with cyclic
carbonate.
81
This provides a useful way to obtain non-isocyanate polyurethanes.
Linear non-isocyanate polyurethanes can be obtained by the reaction of
bifunctional five-membered aliphatic cyclic carbonates with diamines.
109,101
Optically
active poly(hydroxyurethane)s with M
n
of 11,000-24,000 were prepared by the reaction
of L-Lysine with bifunctional five-membered cyclic carbonate.
102
A series of
polyurethanes with M
n
of 6,000-9,000 and relatively low PDI around of 1.5 were
obtained by the polyaddition of phenoxycarbonyloxymethyl ethylene carbonate with
diamines.
103
Polyhydroxyurethane can also be prepared in high yields by the reaction of
the bis(cyclic carbonates) with diamines in aqueous media.
104
A network of non-
isocyanate polyurethanes can be obtained when multifunctional cyclic carbonate
oligomers are used in the reaction with multifunctional primary amines.
108

The poly(cyclic carbonate)s were usually prepared by the reaction of
poly(epoxide)s under CO
2
in the presence of catalyst.
101
Most of poly(epoxide)s for non-
isocyanate polyurethane synthesis reported are low molecule monomers. Recently,
epoxidized soybean oil oligomer has been reported as a starting material to prepare non-
isocyanate polyurethanes.
100
Polyester is a widely used polyol reagent to prepare
polyurethanes by reaction with polyisocyanates.
34
Here, our interest is the preparation of
non-isocyanate polyurethanes. In best of our knowledge there is no report of the synthesis
of non-isocyanate polyurethanes by using epoxidized polyester oligomer as starting
material. In this chapter, hydroxyl terminated polyester was first prepared, then
96

epoxidized polyester was prepared from the hydroxyl terminated polyester with the
epichlorohydrin under the catalysts, and lastly, cyclic carbonate terminated polyester was
synthesized from the reaction of epoxidized polyester and the carbon dioxide. The
hydroxyl terminated, epoxidized terminated, and cyclic carbonate terminated polyesters
were characterized by FTIR and NMR. Non-isocyanate polyurethane coatings were
prepared by the thermo-curing of the cyclic carbonate terminated polyester and
polyamine.
5.3 Materials
Materials: Adipic Acid (AA), p-xylene, 1,6 hexane diol (HD), trimethylolpropane
(TMP), dibutyl tin oxide (DBTO), zinc perchlorate hexahydrate, tetrabutylammonium
bromide (TBAB), epichlorohydrin (>99%), isophorone diamine (>98%), sodium
hydroxide(>97%), acetone, and dichloromethane, all Aldrich products were used as
received.
5.4 Characterization
The FT-IR spectra of the hydroxyl terminated, epoxidized terminated, and cyclic
carbonate terminated polyester were measured in a Nicolet 380 FTIR spectrophotometer.
The results were analyzed using OMNIC software. The NMR spectrum of the hydroxyl
terminated, epoxidized, and cyclic carbonate terminated polyester were taken in a Varian
Mercury 300 MHz spectrophotometer.
97

5.5 Synthesis
In this synthsis part, hydroxyl terminated, epoxy terminated, and cyclic carbonate
terminated polyesters were prepared.
5.5.1 Synthesis of hydroxyl terminated polyester (H-PE)
Adpic acid (AA) (146.14g, 1 mol), 1,6 hexane diol (HD) (118.18 g, 1mol) and
Trimethylolpropane (TMP) (67.09 g, 0.5mol) were taken in a 500 ml four-neck round
bottom flask which was equipped with a mechanical stirrer, a gas inlet, a temperature
controller, a Dean-Stark trap and a condenser. The reaction proceeded under argon to
minimize oxidative degradation. To accelerate the reaction, 0.4 wt % of DBTO, a
transesterification catalyst, was used. Then, 3 wt % of p-xylene was also added into the
reaction mixture to remove water from the resin as azeotropic mixture. The reaction
temperature was carefully controlled using a temperature controller and a thermocouple
in order to minimize evaporation of diol. The temperature of the mixture was increased
from 20-150
0
C at a rate of 4.3
0
C/min, and then from 150-210
0
C at a rate of 0.25
0
C/min.
The final temperature was held until the resin had an acid number measured by titration
less than or equal to 10 mg KOH/g resin. The hydroxyl number of polyesters (297 mg
KOH/g resin) was determined by ASTM method (ASTM D 1957-86).
5.5.2 Synthesis of epoxidized polyester (E-PE)
Epichlorohydrin (17.135g) was added carefully while stirring the hydroxyl
terminated polyester H-PE (50 g) and zinc perchlorate hexahydrate (1.5 g) mixture

at 80
0
C. After 20 hours reaction, the temperature was cooled down to 60
0
C and 300 mL
acetone was added. Then, 23.15 g of NaOH (32% aqueous solution) was added drop wise.
98

Stirring was continued for 5 hours. Filtered while hot and the solvent were removed
under reduced pressure to yield epoxidized polyester (E-PE).
5.5.3 Synthesis of cyclic carbonate polyester (CC-PE)
Epoxidized polyester (E-PE) (20g) and the catalyst tetrabutylammonium bromide
(TBAB) (0.654 g) were placed in a 50 mL reactor, stirred, and heated. The reaction was
carried out at 110
0
C for 12 hours to yield cyclic carbonate polyester (CC-PE). The
conversion of epoxy to carbonate was monitored by IR spectroscopy.
5.5.4 Polyurethane preparation
0.25 g of cyclic carbonate polyester (CC-PE) was placed in a 2 mL vial followed
by isophorone diamine and acetone and mixed thoroughly. The viscous solution was
poured into a mold and heated at 70
0
C for 24 h.
5.6 Results and discussion
Epoxidized polyester (E-PE) was obtained in the reaction of the hydroxyl
terminated polyester (H-PE) with epichlorohydrin by using zinc perchlorate hexahydrate
as catalyst. Figure 5- 1 gives the overall synthetic approach by using hydroxyl terminated
polyester as starting materials to prepare non-isocyanate polyurethane. FTIR results in
Figure 5- 2b show the new peaks at 909 and 854 cm
-1
formation which correspond the
epoxy group.
1
H NMR in Figure 5- 3b and
13
C NMR in Figure 5- 4b also show the epoxy
group formation.
Cyclic carbonate polyester (CC-PE) was prepared from the epoxidized polyester
(E-PE) and carbon dioxide. FTIR results in Figure 5- 2c show the new peak at 1802 cm
-1

99

formation which correspond cyclic carbonate, and the peaks at 909 and 854 cm
-1

disappearance which correspond the epoxy group.
1
H NMR in Figure 5- 3c and
13
C NMR
in Figure 5- 4c also show the cyclic carbonate group formation and epoxy group
disappearance. H-PE has a Brookfield viscosity of 5800 mPas, the E-PE has a Brookfield
viscosity of 1100 mPas, and the CC-PE has a Brookfield viscosity of 9400 mPas.


Figure 5- 1 Non-isocyanate polyurethane preparation procedure



R OH
x
R' NH
2
y
O
Cl
R
O
O
x
CO
2
R
O
O
O
O
x
Thermosetting
PU coating
Polyol
+
Polyacid
H-PE
E-PE
CC-PE
100


Figure 5- 2 FTIR spectra of hyrdroxyl terminated polyester (H-PE), epoxidized polyester
(E-PE) and cyclic carbonate polyester (CC-PE)


Figure 5- 3
1
H NMR spectra (300 MHz, CDCl
3
) of hyrdroxyl terminated polyester (H-
PE), epoxidized polyester (E-PE) and cyclic carbonate polyester (CC-PE)



2200 2000 1800 1600 1400 1200 1000 800 600
b. E-PE
c. CC-PE
a. H-PE
1802


T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm
-1
)
101


Figure 5- 4
13
C NMR spectra (300 MHz, CDCl
3
) of hyrdroxyl terminated polyester (H-
PE), epoxidized polyester (E-PE) and cyclic carbonate polyester (CC-PE)

The CC-PE formation with time was monitored by using IR spectroscopy by
focusing on the appearance of a new peak at 1805 cm
-1
due to the carbonyl of the cyclic
carbonate moieties. As shown in Figure 5- 5, the peak intensity in 1805 cm
-1
keep
increase with the reaction time.
102


Figure 5- 5 FTIR spectra of CC-PE formation with time
The polyurethane was prepared by the reaction of cyclic carbonate polyester (CC-
PE) with isophorone diamine at 70
0
C. The non-isocyanate polyurethane formation with
time was monitored by focusing on the disappearance of cyclic carbonate peak at 1805
cm
-1
. Figure 5- 6 shows the polyurethane formation with time when the mole ratio of
isophorone diamine (IPDA) to CC-PE is fixed (the mole ratio of amine to cyclic
carbonate is 1.25). It shows that most of the cyclic carbonate was disappeared after 24
hours reaction. Figure 5- 7 shows the polyurethane formation with different amine to
cyclic carbonate ratio when curing time is fixed. It shows that when the amine to cyclic
carbonate mole ratio is 1.25, most of the cyclic carbonate was disappeared after 24 hours
reaction.

4000 3000 2000 1000 0
g. 12 hr
f. 10 hr
e. 8 hr
d. 6 hr
c. 4 hr
b. 2 hr
a. 0 hr
1802


T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm
-1
)
103


Figure 5- 6 FTIR spectra of non-isocyanate polyurethane formation with time by using
CC-PE cured with IPDA under 70
o
C (NH
2
/CC=1.25)


Figure 5- 7 FTIR spectra of non-isocyanate polyurethane formation at different amine to
cyclic carbonate ratio by using CC-PE cured with IPDA under 70
o
C 24h

4000 3500 3000 2500 2000 1500 1000 500
1802
d. 46 hr
c. 24 hr
b. 19 hr
a. 4 hr


T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm
-1
)

4000 3500 3000 2500 2000 1500 1000 500
e.NH
2
/CC = 1.5
d.NH
2
/CC = 1.25
c.NH
2
/CC = 1.0
b.NH
2
/CC = 0.75
1802
a.NH
2
/CC = 0.5


T
r
a
n
s
m
i
t
t
a
n
c
e
Wavenumber (cm
-1
)
104

5.7 Conclusions
In conclusions, the hydroxyl terminated, epoxidized, and cyclic carbonate
terminated polyesters were synthesized and characterized by NMR. The cyclic carbonate
terminated polyester formation with time was monitored by using IR spectroscopy. Non-
isocyanate polyurethane coatings were prepared by the thermo-curing of the cyclic
carbonate terminated polyester and polyamine.
105

CHAPTER VI

PHOTOPOLYMERIZATION OF THE NON-ISOCYANATE URETHANE
DIMETHACRYLATES AS REACTIVE DILUENTS FOR UV-CURABLE COATING

6.1 Abstract
The photopolymerization kinetics of non-isocyanate urethane dimethacrylates
(NUDMA) were studied. Three NUDMA reactive diluents were synthesized from
urethane diols which were prepared from the reaction of cyclic carbonate with amino
alcohol. The effect of the NUDMA type and content on the viscosity of the acrylated
polyester (APE) oligomer was investigated by Brookfield viscometer. The real time
Fourier transform infrared spectroscopy (FTIR) was used to investigate the
photopolymerization kinetics of reactive diluents and photointiator (PI). PI Darocur 4265
showed highest overall conversion and maximum polymerization rate. The
polymerization conversion and maximum polymerization rate increase with increasing
initiator concentration in the range from 0.5 % to 4.0 %. The formulation system
containing both the APE oligomer and NUDMA reactive dilutes showed higher
polymerization overall conversion and maximum polymerization rate than APE oligomer.
106

6.2 Introduction
UV-curable coatings offer many advantages, such as rapid curing, high-energy
efficiency and low volatile organic content (VOC)
153
. Photopolymerization can occur at
relatively low temperature with a nature of ultrafast curing, which makes UV-curable
coating suitable for a widely application in the market sectors where temperature
sensitive substrates are coated, like wood, paper and plastics.
154, 155
Most UV-curable
coating systems are free radical based on acrylated oligomers formulated with (meth)
acrylate reactive diluents.
Reactive diluent is an important component of the UV-curable coating
formulation solutions. Reactive diluent has two functions. One is to dilute the viscosity of
the oligomer and thus facilitate the coating application process. The second functionality
is to copolymerize with oligomer chemically bound into the final crosslinked film and
thus adjust the final film properties.
156, 157

The reactive diluent affects the film properties, cure rates and degree of
polymerization. It is generally considered that mono-functional reactive diluent like 2-
ethylhexyl acrylate makes the film softer with reduced mechanical strength, whereas
multi-functional reactive diluent induces higher mechanical strength to the film with
relatively hard character.
157

Recently, a novel reactive diluent named as GPTEMA with long-branched chain
was synthesized through the reaction of glycerol propoxylate triglycidyl ether (GPTE)
and methacrylic acid. This reactive diluent can reduce the polymerization shrinkage and
improve the double bond conversion.
158
The addition of the tripropane glycol diacrylate
(TPGDA) reactive diluent into the UV curable polycarbosilane system could accelerate
107

the curing reaction rate of the polymer.
159
The addition of vinyl pyrrolidinone reactive
diluent into the polyesterpolyol acrylates system could increase the mechanical property
of the polymer.
160

Photopolymerization kinetics of methacrylate reactive diluents
161, 162, 163
and
oligomers
164
have been widely studied. The effects of the reactive diluents on the
oligomers photopolymerization kinetics were also investigated.
165, 166
Generally, the
reactivity of the function groups determines the rate of polymerization, whereas the
chemical structure and the functionality of both the oligomer and the reactive diluent
determine the final degree of polymerization.
167
It is generally observed that past an
optimum point an increase in the functionality will lead to the decrease in final
conversion. This is due to the fact that the increase in functionality will lead to increase in
the viscosity and crosslink density with the resulting gel effect, which set a limit to the
extent of conversion.
168

The incorporation of urethane function group into the coating system could make
the crosslinked film with excellent physical and mechanical properties such as high
impact and tensile strength, abrasion resistance and toughness combined with excellent
resistance to chemicals and solvent.
168, 169, 170, 171, 172, 173
However urethane was usually
formed via the reaction of the isocyanate and polyol, which makes urethane
environmentally less attractive. Recently, urethane dimethacrylate monomer prepared via
the non-isocyanate route from the reaction of a urethane diol with methacrylic anhydride
has been reported.
174, 175, 176
The urethane dimethacrylate monomer photopolymerization
has been reported using photoinitiated differential scanning calorimetry.
174
Up to now, no
systematic investigation of the kinetic of the urethane dimethacrylates reactive diluents in
108

coating system has been studied by real time Fourier transform infrared spectroscopy
(FTIR). It is known that UV-curable acrylated polyester shows good properties such as
high hardness, toughness, solvent resistant, and an excellent ratio value of properties to
cost. It has been widely used as a oligomer for UV-curable coatings.
177

In this study, acrylated polyester (APE) oligomer and non-isocyanate urethane
dimethacrylate (NUDMA) reactive diluents were synthesized, and characterized by
1
H
nuclear magnetic resonance (NMR),
13
C NMR. The effects of the NUDMA reactive
diluent content and type on the viscosity of the APE oligomer were studied. The effects
of the photointiator content and type on the NUDMA reactive diluents
photopolymerization kinetics were investigated by real time Fourier transform infrared
spectroscopy (FTIR).
6.3 Materials
Adipic Acid (AA), isophthalic acid (IPA), 1, 6 hexane diol (HD),
trimethylolpropane (TMP), p-xylene, dibutyl tin oxide (DBTO), ethylene carbonate (EC),
propylene carbonate (PC), 2-aminoethanol (EOA), 3-aminopropanol (POA), methacrylic
anhydride (MAA, 94%), dichloromethane, hydroquinone, Triethylene diamine (TEA) all
Aldrich products were used as received. 4-(dimethyl-amino)pyridine (DMAP) was
obtained from Acros Organics. Photoinitiators Irgacure 184, Irgacure 500, Darocur 1173,
Irgacure 819, and Darocur 4265 were obtained from Ciba Specialty Chemical, NY.
Ethylene glycol dimethacrylate (EGDMA) was obtained from Sartomer USA, PA.
109

6.4 Instrumentation and characterization
1
H NMR and
13
C NMR spectra were recorded on a Mercury 300 MHz
spectrometer (Varian) in CDCl
3
as a solvent for APE, DMSO as a solvent for NUDMA.
Fourier transform infrared (FTIR) spectroscopy was performed on a Nicolet 380 (Thermo
Electron Corp). Real time FTIR was recorded with an external Lesco Super Spot MKII
UV Source. The samples for the real time FTIR measurement were cast on a KBr plate as
a thin film around 25 m. The UV-light was delivered through a flexible light guide. The
KBr plate was positioned at an angle of 45
o
and at a distance of 2 cm to the end of the
light guide to facilitate full KBr plate exposure to UV-light. The UV-light intensity was
measured to be 20 mW/cm
2
(Digital UV AB Light Meter, General UV513AB). Viscosity
measurement was accomplished by Laboratory Brookfield viscometer (DVII+ PRO
Digital) at room temperature. A spindle SC4-25 was used at a shear rate of 10 s
-1
.
6.5 Synthesis
In this synthsis part, three different kinds of urethane diols and corresponding
urethane dimethacrylates were synthesized as reactive diluents. Acrylated polyester was
synthesized as oligomer.
6.5.1 Synthesis of non-isocyanate urethane diols
EOAEC urethane diol preparation: Ethylene carbonate (88.06 g, 1.00 mol) was
dissolved in 100 mL dichloromethane, and such solution was drop added into the 2-
aminoethanol (61.08 g, 1.00 mol) and dichloromethane (200 mL) mixture at 0
o
C. After
finish adding, the mixture was stirred at room temperature for 24 hour. The slightly
yellow liquid (yield: 98%) was got by rot vaporing the dichloromethane.
1
H NMR (300
110

MHz, DMSO-d
6
) (ppm) = 3.03 (q, -CH
2
NH-), 3.35 (m, -OCH
2
CH
2
NH-), 3.52 (m, -
OCH
2
CH
2
OH), 3.94 (t, -OCH
2
CH
2
OH), 4.59 - 4.69 (m, -OH), 6.97 (t, -NHCOO-).
13
C
NMR (300 MHz, DMSO-d
6
) (ppm) = 43.06 (-CH
2
NH-), 59.60 (-CH
2
CH
2
OH), 60.08
(HOCH
2
CH
2
-), 65.64 (-COOCH
2
-), 156.56 (C=O, carbamate).
POAEC urethane diol preparation: POAEC diol was prepared using the same
procedure as for EOAEC diol. From ethylene carbonate (88.06 g, 1.00 mol) and 3-
aminopropanol (75.11 g, 1.00 mol), product POAEC (149.04 g) was obtained (91%
yield). The final product was a clear liquid.
1
H NMR (300 MHz, DMSO-d
6
) (ppm) =
1.53 (t, -CH
2
CH
2
CH
2
-), 2.98 - 3.09 (q, -CH
2
NH-), 3.36 - 3.43 (m, -OCH
2
CH
2
NH-), 3.52
(m, -OCH
2
CH
2
OH), 3.93 (m, -OCH
2
CH
2
OH), 4.49 - 4.69 (m, -OH), 7.00(m, -NHCOO-).
13
C NMR (300 MHz, DMSO-d
6
) (ppm) = 32.81 (-CH
2
CH
2
CH
2
-), 37.69 (-CH
2
NH-),
58.62-59.68 (-CH
2
CH
2
OH), 65.64 (-COOCH
2
-), 156.57 (C=O, carbamate).
POAPC urethane diol preparation: POAPC diol was prepared using the same
procedure as for EOAEC diol. From propylene carbonate (102.09 g, 1.00 mol) and 3-
aminopropanol (75.11 g, 1.00 mol), POAPC (131.20 g) product was obtained (74% yield).
The final product was a clear liquid.
1
H NMR (300 MHz, DMSO-d
6
) (ppm) = 0.97 -
1.14 (m, -CH
2
CHCH
3
), 1.53 (quin, -CH
2
CH
2
CH
2
-), 2.93 - 3.09 (m, -CH
2
NH-), 3.30 -
3.44 (m, -OCH
2
CH
2
-), 4.50 - 4.67 (m, -OCH
2
CH(CH
3
)O-, -OCH(CH
3
)CH
2
O-), 6.88 -
7.05 (m, NHCOO-).
13
C NMR (300 MHz, DMSO-d
6
) (ppm) = 16.98 (-
OCH
2
CH(CH
3
)OH), 17.00 (-OCH(CH
3
)CH
2
OH), 32.77 (m, -CH
2
CH
2
CH
2
-), 37.65 (-
CH
2
NH-), 58.54 (HOCH
2
CH
2
-), 64.09 (-OCH
2
CH(CH
3
)O-), 64.54 (OCH(CH
3
)CH
2
O-),
68.97 (-OCH(CH
3
)CH
2
O-), 70.86 (-OCH
2
CH(CH
3
)O-), 156.18 -156.45 (C=O, carbamate)
111

6.5.2 Synthesis of non-isocyanate urethane dimethacrylate

EOAED urethane dimethacrylate preparation: Urethane diol EOA-EC (14.9 g, 0.1
mol) was dissolved in dichloromethane (300 mL) at 0
o
C, 4-(dimethyl-amino)pyridine
(DMAP) catalyst (122 mg, 1 mmol), and 0.05 wt % hydroquinone (inhibitor) (28 mg)
were added in, followed by drop addition of triethylene diamine (TEA) (28.3 g, 0.28 mol),
and then drop addition of methacrylic anhydride (39.4g, 0.24 mol) under the N
2

atmosphere. The reaction mixture was stirred at 0
o
C for 24 h. Then, saturated sodium
bicarbonate solution (294.7 g) was dropped added to get two phase separated mixture.
The product (top layer) was collected, washed with brine (300 mL 3) and water (300
mL 2), and dried in anhydrous magnesium sulphate. After dichloromethane was
evaporated, the final liquid product was pale yellow color (yield: 42%).
1
H NMR (300
MHz, DMSO-d
6
) (ppm) = 1.86(m, 6 H, -CH
3
), 3.27 (qd, J = 5.67, 1.39 Hz, 2 H, -
CH
2
NH-), 4.07 (td, J=5.57, 1.63 Hz, 2 H,-OCH
2
CH
2
O-), 4.12 (m, 2 H, -OCH
2
CH
2
NH-),
4.14 - 4.30 (m, 2 H,-OCH
2
CH
2
O-), 5.62 - 5.78 (m, 2 H, trans C=CH
2
) 5.98 - 6.12 (m, 2 H,
cis C=CH
2
), 7.42(t, 1 H, -NHCOO-).
13
C NMR (300 MHz, DMSO-d
6
) (ppm) = 18.11 (-
CH
3
), 39.79 (-CH
2
NH-), 62.11 (-NHCOOCH
2
-), 63.32 (-CH
2
CH
2
O-), 63.49 (-COOCH
2
-),
126.18 (C=CH
2
), 136.10 (C=CH
2
), 156.46 (C=O, carbamate), 166.67 (C=O, ester).
POAED urethane dimethacrylate preparation: POAED urethane dimethacrylate
was prepared using the same procedure as for EOAED dimethacrylate. From of POAEC
(16.3 g, 0.1 mol) and methacrylic anhydride (39.4 g, 0.24 mol), POAED (24.01 g)
product was obtained (82% yield). The final product was a pale liquid with lower
viscosity than POAEC diol.
1
H NMR (300 MHz, DMSO-d
6
) (ppm) = 1.75 (m, -
CH
2
CH
2
CH
2
-), 1.86(m, -CH
3
), 2.99 - 3.15 (m, -CH
2
NH-), 4.07 (td, -OCH
2
CH
2
O-), 4.12
112

(m, 2 H, -OCH
2
CH
2
NH-), 4.08 (m, COOCH
2
CH
2
-), 4.14 - 4.29 (m,-OCH
2
CH
2
O-),
5.66(dd, trans C=CH
2
), 6.02 (d, cis C=CH
2
), 7.29 (t, -NHCOO-).
13
C NMR (300 MHz,
DMSO-d
6
) (ppm) = 17.92 (-CH
3
), 28.49 (m, -CH
2
CH
2
CH
2
-), 37.18 (-CH
2
NH-), 61.68
(-NHCOOCH
2
-), 62.05 (-COOCH
2
-), 62.27 (-CH
2
CH
2
O-), 125.93(C=CH
2
), 136.00
(C=CH
2
), 156.02 (C=O, carbamate), 166.43 (C=O, ester)
POAPD urethane dimethacrylate preparation: POAPD urethane dimethacrylate
was prepared using the same procedure as for EOAED dimethacrylate. From of POAEC
(17.7 g, 0.1 mol) and methacrylic anhydride (39.4 g, 0.24 mol), POAPD (22.05 g)
product was obtained (70% yield). The final product was a pale liquid with lower
viscosity than POAPC diol.
1
H NMR (300 MHz, DMSO-d
6
) (ppm) = 1.18 (dd, -
CH
2
CHCH
3
), 1.74 (quin, -CH
2
CH
2
CH
2
-), 1.86 (m, -CH
2
=C(CO)CH
3
), 3.06 (q, -CH
2
NH-),
4.13 (m, -COOCH
2
CH
2
), 4.01 - 4.13 (m, -OCH
2
CH(CH
3
)O-, -OCH(CH
3
)CH
2
O-), 4.89 -
5.06 (m, -OCH
2
CH(CH
3
)O-, -OCH(CH
3
)CH
2
O-), 5.65(dt, trans C=CH
2
), 6.01 (s, cis
C=CH
2
), 7.29 (m, -NHCOO-).
13
C NMR (300 MHz, DMSO-d
6
) (ppm) = 16.51 (-
CH
2
CHCH
3
), 17.86 (-CH
2
=C(CO)CH
3
), 28.57 (-CH
2
CH
2
CH
2
-), 37.08 (-CH
2
NH-),
62.01(-COOCH
2
-), 64.41 (-OCH(CH
3
)CH
2
O-), 66.46 (-OCH
2
CH(CH
3
)O-), 67.42 (-
OCH
2
CH(CH
3
)O-), 68.94 (-OCH(CH
3
)CH
2
O-), 125.86 (C=CH
2
), 135.98 (C=CH
2
),
155.69 (C=O, carbamate), 166.50 (C=O, ester).
6.5.3 Synthesis of the acrylated polyester (APE) oligomer
The synthesis of acrylated polyester oligomer consists of two steps illustrated in
Figure 6-9. In the first step, hydroxyl terminated polyester polyol was prepared by using
excess diol. The molar ratio of alcohol to acid is 11:8. Adpic acid (AA) (100 g, 0.6 mol),
isophthalic acid (IPA) (113.67 g, 0.68 mol), 1,6 hexane diol (HD) (161.71 g, 1.37 mol)
113

and trimethylolpropane (TMP) (45.90 g, 0.34 mol) were taken in a 500 mL four-neck
round bottom flask which was equipped with a mechanical stirrer, a gas inlet, a
temperature controller, a Dean-Stark trap and a condenser. The reaction proceeded under
argon to minimize oxidative degradation. To accelerate the reaction, 0.4 wt % of DBTO,
a transesterification catalyst, was used. Then, 3 wt % of p-xylene was also added into the
reaction mixture to remove water from the resin as azeotropic mixture. The reaction
temperature was carefully controlled using a temperature controller and a thermocouple
in order to minimize evaporation of diol. The temperature of the mixture was increased
from 20-150
o
C at a rate of 4.3
o
C /min, and then from 150-210
o
C at a rate of 0.25
o
C/min. The final temperature was held until the resin had an acid number measured by
titration less than or equal to 10 mg KOH/g resin. The hydroxyl number of polyesters
(160.4 mg KOH/g resin) was determined by ASTM method (ASTM D 1957-86).
1
H
NMR (300 MHz, CHLOROFORM-d) (ppm) = 0.92 (m, -CH
2
CH
3
), 1.33 - 1.47 (m, -O
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
O-, -CCH
2
CH
3
), 1.50 - 1.66 (m, OCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
O),
1.72 - 1.85(m, -OCO CH
2
CH
2
CH
2
CH
2
COO-), 2.29 (m, -OCO CH
2
CH
2
CH
2
CH
2
COO-),
3.98 - 4.14 (m, RCOOCH
2
-, R is aliphatic group), 4.26 - 4.43 (m, RCOOCH
2
-, R is
aromatic group), 7.50- 8.71 (m, Ar-H)
In the second step, the temperature was reduced to 120
o
C. Acrylic acid (AA, the
mole ratio of the acid in the AA to the hydroxyl in the polyester polyol kept at 1.05), 1
wt % p-toluene sulphonic acid (p-TSA, catalyst) and 0.05 wt % hydroquinone (inhibitor)
(based on the total amount of the polyester polyol and acrylic acid) were added in, the
temperature was maintained at 120
o
C for 14h. Then, 1.5 wt % of 3- methyl-3-
hydroxymethyl-oxetane was added in, and maintained at 120
o
C for another 20 min. Then
114

solvent and residual were removed in vacuo resulting in a light yellow acrylated polyester
oligomer.
1
H NMR (300 MHz, CHLOROFORM-d) (ppm) = 0.92 (m, -CH
2
CH
3
), 1.33 -
1.47 (m, -O CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
O-, -CCH
2
CH
3
), 1.50 - 1.66 (m, -
OCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
O-), 1.72 - 1.85(m, -OCO CH
2
CH
2
CH
2
CH
2
COO-), 2.29 (m, -
OCO CH
2
CH
2
CH
2
CH
2
COO-), 3.57 -3.69 (m, CH
2
-OH), 3.98 - 4.14 (m, RCOOCH
2
-, R
is aliphatic group), 4.26 - 4.43 (m, RCOOCH
2
-, R is aromatic group), 5.74 - 5.89 (m,
trans C=CH
2
), 6.03-6.14 (m, OCOCH= CH
2
), 6.31 - 6.44 (m, cis C=CH
2
),7.50- 8.71 (m,
Ar-H). The average molecular weight was found to be Mn = 3500, with a PDI = 1.8 via
GPC.
6.6 Coating formulation
For neat reactive diluent photopolymerization kinetics study, formulation was
prepared by mixing selected reactive diluent with different photoinitiator type and
content. For study the effect of the reactive diluent on the acrylated polyester (APE)
oligomer photopolymerization kinetics, formulation was prepared by mixing selected
reactive diluent and APE oligomer with different content including 2 wt% of Darocur
4265 based on the total formulation. The chemical structures of the photoinitiators were
depicted in Figure 6- 1.
115


Figure 6- 1 Photoinitiators chemicals structure
6.7 Results and discussion
The overall object of this study is to prepare non-isocyanate urethane
dimethacrylates (NUDMA) and investigate their potential applications as reactive
diluents for UV-curable coatings, by studying the effect of NUDMA type and content on
the viscosity of the oligomer and photopolymerization kinetics of the NUDMA. The
commonly used reactive diluent ethylene glycol dimethacrylate (EGDMA) was also
chosen to compare with the NUDMA reactive diluents.

P
O O
O
OH +
O
OH
O
+
P
O O O
O
OH
a. Darocur 4265
c. Irgacure 819, the main component of Irgacure 2100
b. Irgacure 500
d. Darocur 1173
116

The NUDMA reactive diluents were prepared from the reaction of urethane diols
and methacrylic anhydride. The urethane diols were synthesized from the reaction of
amino alcohols with cyclic carbonate via non-isocyanate route shown in Figure 6- 2.

Figure 6- 2 UDMA reactive diluents synthesis scheme

HO
R
NH
2
O O
O
HO
R
H
N O
OH
O
O
O O
+
O
R
H
N O
O
O O
O
R'
R'
O
R
H
N O
O
O O
O
R'
+
Reactants
Products
R R'
Entry
1 CH
2
CH
2
H EOAED
2
CH
2
CH
2
CH
2
H POAED
3
CH
2
CH
2
CH
2
CH
3
POAPD
117

To investigate the NUDMA type and content on the viscosity of the oligomer,
and compare NUDMA with conventional EGDMA reactive diluent, coating formulations
containing different reactive diluents and concentration were prepared and corresponding
viscosity properties were studied by Brookfield viscometer.
6.7.1 Preparation of reactive diluents and oligomer
In this preparation part, three different kinds of of non-isocyanate urethane
dimethacrylates were prepared as reactive diluents. The acrylated polyester was prepared
as the oligomer.
6.7.1.1 Preparation of non-isocyanate urethane dimethacrylate reactive diluents
The synthesis of non-isocyanate urethane dimethacrylate consists of two steps. In
the first step, urethane diol was prepared by modification of the Assumptions
procedure.
174
The reaction time was extended from 16 h to 24 h, and yield was increased
from 87% to 91% for POAEC diol synthesis. It has been reported that urethane diols
prepared from reaction of linear diamine like 1,6-hexanediamine with cyclic carbonate
were solid state.
174, 178
While urethane diols prepared from the reaction of the branched
diamine or amino alcohol with cyclic carbonate were liquid state. And the urethane diols
prepared from the branched diamine shows higher viscosity than the one prepared from
the amino alcohol.
174, 179
The aim of this study is to prepare monomers used as reactive
diluents, thus requiring the monomer to be liquid with a relatively low viscosity. As
consequences, only amino-alcohols were chosen as starting materials. All these three
urethane diols EOAEC, POAEC, POAPC prepared were liquid with relatively higher
viscosity than water. The characterization of the synthesized urethane diols were carried
118

out by
1
H NMR and
13
C NMR. The
1
H NMR spectra in Figure 6- 3a, 6- 4a and 6- 5a
showed two resonances at 6.88 - 7.05 indicating the presence of protons from urethane
group, which correspond to the pseudo E and Z urethane conformer.
174, 180


Figure 6- 3 NMR of EOAEC urethane diol, (a) 1H NMR and (b) 13C NMR


Figure 6- 4 NMR of POAEC urethane diol, (a)
1
H NMR and (b)
13
C NMR

10 9 8 7 6 5 4 3 2 1 0
OH
O
H
N
O
HO
1
3
4
6
7
5
2
Chemical Shift (ppm)
3 6
1
DMSO
2
7
4

200 180 160 140 120 100 80 60 40 20 0
OH
O
H
N
O
HO
1
3
4
6
7
5
2
Chemical Shift (ppm)
6
DMSO
2,7
3
5

10 9 8 7 6 5 4 3 2 1 0
OH
O
H
N
O
HO
1 3
4
6
7
8
5
2
Chemical Shift (ppm)
3
1
2
7
4
8
5

200 180 160 140 120 100 80 60 40 20 0
OH
O
H
N
O
HO
1 3
4
6
7
8
5
2
Chemical Shift (ppm)
DMSO
8, 2
3
6
4
7
a.
b.
a.
b.
119


Figure 6- 5 NMR of POAPC urethane diol, (a)
1
H NMR and (b)
13
C NMR
In the second step, urethane dimethacrylate was prepared by modification of
Assumptions procedure.
174
In this study, the 4-(dimethyl-amino)pyridine (DMAP)
catalyst amount was reduced from 10 mol% to 1 mol%, triethylene diamine (TEA) was
added to accelerate the reaction of urethane diols with methacrylic anhydride. 0.05 wt %
inhibitor hydroquinone based on total reactants weight was also added to prevent the
polymerization of the double bonds. The yield was increased from 40% to 82% for
POAED urethane dimethacrylate synthesis as compared with Assumptions procedure
174
.
The characterization of the synthesized urethane dimethacrylates were carried out by
1
H
NMR and
13
C NMR. The
1
H NMR spectra in Figure 6- 6a, 6- 7a and 6- 8a showed two
resonances at = 5.7 and 6.0 ppm indicating the presence of protons from the double
bond of a methacrylate group. The
1
C NMR spectra in Figure 6- 6b, 6- 7b and 6- 8b
showed two resonances at = 126 and 136 ppm indicating the presence of carbons from
the double bond of a methacrylate group.
174, 180


8 7 6 5 4 3 2 1 0
OH
O
H
N
O
HO
OH
O
H
N
O
HO
1
6 7
8
5
9
2
3
4
7'
8'
9'
Chemical Shift (ppm)
3
1
2
7
4
8
5
8'
7',7,9',9

200 180 160 140 120 100 80 60 40 20 0
OH
O
H
N
O
HO
OH
O
H
N
O
HO
1
6 7
8
5
9
2
3
4
7'
8'
9'
Chemical Shift (ppm)
DMSO
8 3
6
4
7
8'
2
9
9'
7'
a.
b.
120


Figure 6- 6 NMR of EOAED urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR

Figure 6- 7 NMR of POAED urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR


Figure 6- 8 NMR of POAPD urethane dimethacrylate, (a)
1
H NMR and (b)
13
C NMR

10 9 8 7 6 5 4 3 2 1 0
O
O N
H
O
O
O
O
1
3
4
6
7
8
H
H
H
H
1
3
5
2 2
Chemical Shift (ppm)
3
6
2 1
5
7
8, 4

200 180 160 140 120 100 80 60 40 20 0
O
O N
H
O
O
O
O
1
3
4
6
7
8
1
3
4
5 9
2 2
Chemical Shift (ppm)
1
2
3
4
5
6
7
8
9

200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
9
11
8
10
O
H
N O
O
O O
O
1
3
4
6
7
1
3
4
5
2
2
6
1
7
11,5,10
3
4
9
DMSO
2

10 9 8 7 6 5 4 3 2 1 0
10'
12
11'
12'
O
H
N O
O
O O
O
O
H
N O
O
O O
O
9
11
8
10
1
3
4
6
7
1
3
4
5
2
2
Chemical Shift (ppm)
3
6
1 5
7
8
12,12'
10,11'
11,10'
1

200 180 160 140 120 100 80 60 40 20 0
10'
12
11'
12'
O
H
N O
O
O O
O
O
H
N O
O
O O
O
9
11
8
10
1
3
4
6
7
1
3
4
5
2
2
Chemical Shift (ppm)
6
1
7
11',11
10,10'
4
9
DMSO
2
3
12
5
a.
b.
a.
b.
a.
b.
121

6.7.1.2 Preparation of acrylated polyester (APE) oligomer
A typical poly-condensation technique was used to prepare APE oligomer.
181
The
synthesis of acrylated polyester oligomer consists of two steps illustrated in Figure 6- 9.
In the first step, hydroxyl terminated polyester polyol was prepared by using excess diol
monomer. In the second step, acrylated polyester (APE) was formed via the reaction of
polyester polyol with acrylic acid. The average molecular weight was found to be Mn =
3500, with a PDI = 1.8 via GPC. The characterization of the synthesized polyester polyol
and acrylated polyester were carried out by
1
H NMR as shown in Figure 6- 10. The
1
H
NMR spectra in Figure 6- 10b showed three new resonances at = 5.74, 6.03 and 6.31
ppm indicating the presence of protons from the double bond of an acrylate group. The
peak intensity at = 3.57 -3.69 corresponding to the proton in CH
2
-OH group was lower
in Figure 6- 10a comparing with those in Figure 6- 10b, which indicated that acrylation
reaction was carried out.
122


Figure 6- 9 The synthesis of oligomer acrylated polyester (APE)


HO
OH
HOOC
COOH
HO OH
OH
+
H
O O O O
6
O
4
O
OH
O OH
O O
6
n
COOH
COOH
120
o
C/14hr
p-TSA
210
o
C
O O O O
6
O
4
O
O
O O
O O
6
n
OH
O
O
O
O
DBTO
123


Figure 6- 10
1
H NMR of (a) polyester polyol and (b) acrylated polyester
6.7.2 Viscosity
The viscosity of the synthesized urethane diols and corresponding urethane
dimethacrylates were investigated by using Brookfield viscometer.
6.7.2.1Viscosity of urethane diols vs urethane dimethacrylates
Viscosity is an important property for a monomer to be as a reactive diluent. The
viscosity of the synthesized urethane diols and corresponding urethane dimethacrylates
were shown in Figure 6- 11. The viscosity of the urethane dimethacrylates was dropped
significantly after methacrylation of the corresponding urethane diols. The viscosity of
POAPC urethane diol was dropped from 2487 to 192 mPas for that of POAPD urethane

10 9 8 7 6 5 4 3 2 1 0
O
11
6
20
O
O
O
O
O
O O
O
O
9
19
8 10
1 3
4
18 7 5
2
n
12
13
14
15
O
6'
1' 3'
4'
5'
2'
16
17
O
O
O
H O
11
6
O
O
O
OH
O
O O
O
O
9
8 10
1 3
4
18 7 5
2
n
12
13
14
15
H O
6'
1' 3'
4'
5'
2'
16
17
5,5',2,2'
Chemical Shift (ppm)
14
3,4,3',4',13
8,9
7,10
1',12
1,11
6',15
16
17
18
20
19
20
124

dimethacrylate. The viscosity of EOAEC urethane diol was dropped from 786 to 57
mPas for that of EOAED urethane dimethacrylate. The viscosity of POAEC urethane
diol was dropped from 818 to 22 mPas for that of POAED urethane dimethacrylate. It
has been reported that urethane diols could be used as reactive diluents and cross-linkers
for high solid coating. The incorporation of the urethane diol could raise the application
solids, increase film hardness, water resistance and exterior durability.
182, 183, 184
So it is
expected that the urethane dimethacrylate with even much lower viscosity could have a
potential application for use as reactive diluent. Compared to the POAED, the EOAED
shows higher viscosity, which could be explained that the shorter chain makes the
molecule stiffer, increasing the viscosity; the POAPD shows higher viscosity, which
could be explained that hindrance effect induces the increase in viscosity due to the
incorporation of the side methyl group making the molecule more bulky. POAPD shows
higher viscosity than the EOAED indicating that the hindrance effect plays a more
important role than the chain spacer effect on the viscosity increase.

Figure 6- 11 The viscosity of the synthesized urethane diols and corresponding urethane
dimethacrylates

POAPC POAPD EOAEC EOAED POAEC POAED
0
500
1000
1500
2000
2500



V
i
s
c
o
s
i
t
y

(
m
P
a
s
)
Diol
Dimethacrylate
125

6.7.2.2 Viscosity of reactive diluents with acrylated polyester (APE)
First, as to be reactive dilutes, the non-isocyanate urethane dimethacrylates
(NUDMA) synthesized are anticipated to reduce the viscosity of the acrylated polyester
(APE) oligomer. The viscosities of the formulations were investigated and compared to
that of the neat APE oligomer. The viscosity was studied as a function of amount and
type of reactive diluent. The commonly used reactive diluent ethylene glycol
dimethacrylate (EGDMA) was chosen to compare with the NUDMA reactive diluents.
The results for this experiment are presented in Figure 6- 12.

Figure 6- 12 Viscosity behavior of neat APE oligomer and APE/reactive diluent mixtures
The viscosity of the APE oligomer used for all runs was found to be 10840 mPas.
As expected, EGDMA and all three NUDMA reactive diluents effectively reduce the
viscosity of the APE oligomer. At 10 wt % loading of reactive diluents, the viscosity of

0 10 20 30 40
10
2
10
3
10
4


V
i
s
c
o
s
i
t
y

(
m
P
a
s
)
Reactive Diluents Concentration (Wt %)
POAPD
EOAED
POAED
EGDMA
126

the formulation was decreased to 6740 mPas (62%) for POAPD, 5586 mPas (52%) for
EOAED, 4886 mPas (45%) for POAED, and 2985 mPas (28%) for EGDMA. The
viscosity of the formulation systems were further decreased with the addition of the
reactive diluents in the loading range of 10 40 wt %.
Compared to the formulation containing EGDMA and APE, the formulation
containing NUDMA and APE always show higher viscosity. These are due to hydrogen
bond formation via the urethane group in the NUDMA system. Among the three
NUDMA reactive diluents, the POAED reactive dilute shows the lowest viscosity
reduction followed by the EOAED and POAPD reactive diluents. NUDMA systems
show higher viscosity than the EGDMA system. The viscosity order of the NUDMA
formulation system follows the same viscosity order of the neat NUDMA reactive diluent.
6.7.3 Kinetics studies by real-time FTIR
It has been widely accepted that the real time FTIR is an excellent tool for
determining both the rate and conversion of the photopolymerization.
185, 186, 187, 188
This
technique offers the opportunity to investigate the kinetics of the photopolymerization by
monitoring the decay of the intensity of the peak at specific wavelength. In this study, the
alkene twisting vibration at 810 cm
-1

185
was used to monitor the double bond conversion.
The conversion of double bond at a given time was calculated from the change in the
absorption peak area as function of time:
189

(6-1)
where

and

were the IR absorbance at specified bands at starting

time and the given time, respectively. In this study, neat NUDMA reactive diluents
127

containing different photoinitiator type and content, and formulation containing NUDMA
reactive diluents and APE oligomer were prepared. Experiments were performed at
ambient temperature at UV-light intensity of 20 mW/cm
2
in the

range of 280-400 nm
(Digital UV AB Light Meter, General UV513AB).
6.7.3.1 Effect of PI type and concentration
It is known that the photoinitiator generates the free-radicals that initiate radical
polymerization of the unsaturated oligomer or reactive diluents. The photoinitiators used
for free radical polymerization reactions has been thoroughly reviewed.
156, 190, 191
The
typical absorption spectra of the common used photoinitiators are listed in the
literature.
156
The chemical structures of the photoinitiators in this study are shown in
Figure 6- 1. In order to investigate the effect of photoinitiators on the neat reactive diluent,
2 wt% of each photoinitiator was added. The double bond conversion was monitored as a
function of time.
Figure 6- 13a shows the effect of PI type on polymerization conversion. All the
initiators have similar photopolymerization behavior and maximum conversion is reached
after 10 sec of irradiation. The highest overall conversion was observed for PI Darocur
4265 (62%), followed in order by Irgacure 819(60%), Darocur 1173(53%), Irgacure
500(32%), Irgacure 184 (23%). The overall conversion for Darocur 4265 and Irgacure
819 were comparatively higher than the rest of other three PI. This can be attributed to
the more proximity of
max
value of Darocur 4265 and Irgacure 819 for n* transition
falling nearer to the major emission line at 365 nm.
156, 166, 192

Figure 13.b shows the effect of PI type on polymerization rate. And the data were
summarized in Table 1. All the initiators have similar photopolymerization behavior and
128

maximum polymerization rate (

) is reached after around 3 sec of irradiation. The

highest polymerization rate was oberserved 0.158 s
-1
for PI Darocur 4265, followed in
order by Irgacure 819 (0.148 s
-1
), Darocur 1173 (0.094 s
-1
), Irgacure 500 (0.047 s
-1
),
Irgacure 184 (0.040 s
-1
). This is in the same order as the overall conversion. It indicates
that strength of photoinitiator absorption of the UV light dominates the maximum
polymerization rate (

).
193
Since PI Darocur 4265 showed highest overall conversion
and maximum polymerization rate, it was chosen as the PI for further
photopolymerization kinetics of reactive diluents and its formulation with APE oligomer.

Figure 6- 13 Polymerization conversion (a) and polymerization rate (b) of EOAED
reactive diluents as a function of exposure time for different type PI with 2 wt %
concentration
Figure 6- 14 shows the effect of PI Darocur 4265 content on the polymerization
conversion and rate of EOAED reactive diluent. And the dada were summarized in Table
1. With increasing initiator concentration in the range from 0.5% to 4.0%, the
polymerization overall conversion was increased from 26 % to 65 %, and maximum
polymerization rate was increased from 0.083 s
-1
to 0.207 s
-1
. This is due to the greater
amount of molecules available for reaction.
188


0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
Irgacure 184
Irgacure 500
Darocur 1173
Irgacure 819
Darocur 4265


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec) Start of irradiation
a.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
Irgacure 184
Irgacure 500
Darocur 1173
Irgacure 819
Darocur 4265


R
a
t
e

(
s
e
c
-
1
)
Time (sec)
b.
129


Figure 6- 14 Polymerization conversion (a) and polymerization rate (b) of EOAED
reactive diluent as a function of exposure time for PI Darocur 4265 with different
concentration
Table 6- 1 Photopolymerization kinetics data as a function of photoinitiator type (with 2
wt %) and photoinitiator Darocur 4265 concentration

Conversion (%)

(s
-1
)
Photoinitiator
Type (2 wt %)


Darocur 4265 55 0.158
Irgacure 819 54 0.148
Darocur 1173 44 0.094
Irgacure 500 27 0.047
Irgacure 184 18 0.040
Darocur 4265
Concentration
(wt %)

0.5 26 0.083
1.0 47 0.131
2.0 55 0.153
3.0 59 0.173
4.0 65 0.207

6.7.3.2 Effect of oligomer and reactive diluents type
The chemical structure of the reactive diluents may affect the polymerization
kinetics. Figure 6- 15 shows the polymerization conversion and rate of APE oligomer and
four different reactive diluents as a function of exposure time at 2.0 wt% PI Darocur 4265
concentration. And the data were summarized in Table 6- 2. The overall conversion for
APE (71%), EGDMA (70%), and POAPD (68%) are similar, which are higher than the
overall conversion for POAED (57%) and EOAED (55%). The maximum polymerization

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
PI 0.5%
PI 1.0%
PI 2.0%
PI 3.0%
PI 4.0%
a.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
0.5%
1.0%
2.0%
3.0%
4.0%


R
a
t
e

(
s
e
c
-
1
)
Time (sec)
b.
130

rate (

) for APE (0.237 s

-1
), EGDMA (0.236 s
-1
) is similar, which is higher than the
one for POAPD (0.181 s
-1
), POAED (0.153 s
-1
) and EOAED (0.153 s
-1
).

Figure 6- 15 Polymerization conversion (a) and polymerization rate (b) of APE oligomer
and four reactive diluents as a function of exposure time at 2.0 wt % PI Darocur 4265
concentration
Table 6- 2 Photopolymerization kinetics data as a function of reactive diluent type and
concentration
Sample Conversion (%)

(s
-1
)
APE 71 0.237
EGDMA 70 0.236
EOAED 55 0.153
POAED 57 0.153
POAPD 68 0.181
EGDMA-10 71 0.236
EGDMA-20 78 0.236
EGDMA-30 77 0.208
EGDMA-40 65 0.152
EOAED-10 74 0.24
EOAED-20 74 0.25
EOAED-30 78 0.233
EOAED-40 80 0.233
POAED-10 77 0.235
POAED-20 77 0.254
POAED-30 88 0.289
POAED-40 92 0.246
POAPD-10 75 0.254
POAPD-20 81 0.267
POAPD-30 82 0.263
POAPD-40 85 0.251

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
APE
EGDMA
EOAED
POAED
POAPD


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
a.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
APE
EGDMA
EOAED
POAED
POAPD


R
a
t
e

(
s
e
c
-
1
)
Time (sec)
b.
131

6.7.3.3 Effect of formulation with different reactive diluents type and concentration
Figure 6- 16 shows the polymerization conversion as a function of exposure time
of the formulation of APE with different reactive diluents. And the data were summarized
in Table 6- 2. For APE oligomer, the overall polymerization conversion was 71%. For
EGDMA system, the overall conversion did not change with the addition of 10 wt%
reactive diluents, increased to the maximum with addition of 20 wt% reactive diluents,
the decreased slightly with addition of 30 wt % reactive diluents, and decreased
apparently with further addition of reactive diluents to 40 wt% reactive diluents. The
overall conversion was 71%, 78%, 77%, and 65% with addition of 10 wt%, 20 wt%, 30
wt%, and 40 wt% of reactive diluents separately. For all the three NUDMA systems, the
overall conversion increased with content of the reactive diluents in the load range of 10-
40 wt%. It indicates that the polymerization conversion of the formulation system was
higher than those of the neat system (either neat oligomer or reactive diluents), except the
EGDMA system with 40 wt % reactive diluents concentration.




132



Figure 6- 16 Polymerization conversion as a function of exposure time of the formulation
of APE with different reactive diluents: (a) EGDMA, (b) EOAED, (c) POAED, and (d)
POAPD
Figure 6- 17 shows the polymerization rate as a function of exposure time of the
formulation of APE with different reactive diluents. And the data were summarized in
Table 6- 2. The effect of the reactive diluents type and content on the maximum
polymerization rate exhibits the similar trends as overall polymerization conversion. For
APE oligomer, the maximum polymerization rate was 0.237 s
-1
. For EGDMA system, the
maximum polymerization rate remained constant with the addition of 10 wt% and 20 wt %
reactive diluents (within experimental error), and decreased with further addition of
reactive diluents to 40 wt % reactive diluents. For all the three NUDMA systems, the
maximum polymerization rate initially increased with addition of reactive diluents, and
reached the maximum in the load of 20 wt% or 30 wt %, then decreased with further

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
APE
EGDMA-10
EGDMA-20
EGDMA-30
EGDMA-40


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
a.

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
APE
EOAED-10
EOAED-20
EOAED-30
EOAED-40


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
b.

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
APE
POAED-10
POAED-20
POAED-30
POAED-40


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
c.

0 20 40 60 80 100 120 140 160 180 200
0
20
40
60
80
100
APE
POAPD-10
POAPD-20
POAPD-30
POAPD-40


C
o
n
v
e
r
s
i
o
n

(
%
)
Time (sec)
d.
133

addition of reactive diluents. Compared with the APE oligomer, all the three NUDMA
system showed higher maximum polymerization rate in the load range of 10-40 wt%
reactive diluents, except for the EOAED system with the reactive diluents concentration
of 30-40 wt%. It indicates that the addition of the NUDMA reactive diluents could
increase the maximum polymerization rate.


Figure 6- 17 Polymerization rate as a function of exposure time of the formulation of
APE with reactive diluents: (a) EGDMA, (b) EOAED, (c) POAED, and (d) POAPD
6.8 Conclusions
Three urethane dimethacrylate monomers were synthesized via a non-isocyanate
route. The addition of the non-isocyanate urethane dimethacrylate could reduce the
viscosity of the acrylated polyester (APE) oligomer dropply. Such urethane
dimethacrylates could use as reactive diluents for UV-curable coating.
photopolymerization kinetics of non-isocyanate urethane dimethacrylates were studied.
PI Darocur 4265 shows highest overall conversion and maximum polymerization rate, it

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
0.30
EGDMA-10
EGDMA-20
EGDMA-30
EGDMA-40
APE


R
a
t
e

(
s
e
c
-1
)
Time (sec)
a.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
0.30
APE
EOAED-10
EOAED-20
EOAED-30
EOAED-40


R
a
t
e

(
s
e
c
-1
)
Time (sec)
b.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
0.30
APE
POAED-10
POAED-20
POAED-30
POAED-40


R
a
t
e

(
s
e
c
-1
)
Time (sec)
c.

0 2 4 6 8 10 12 14 16
0.00
0.05
0.10
0.15
0.20
0.25
0.30
APE
POAPD-10
POAPD-20
POAPD-30
POAPD-40


R
a
t
e

(
s
e
c
-1
)
Time (sec)
d.
134

was chosen as the PI for photopolymerization kinetics of reactive diluents and its
formulation with APE oligomer. The polymerization conversion and maximum
polymerization rate increase with increasing initiator concentration in the range from 0.5 %
to 4.0 %. The reactive diluents non-isocyanate urethane dimethacrylate showed lower
polymerization overall conversion and maximum polymerization rate than APE oligomer.
But formulation system showed higher polymerization overall conversion and maximum
polymerization rate than APE oligomer.
135

CHAPTER VII

MECHANICAL AND FILM PROPERTY OF UV-CURABLE NON-ISOCYANATE
POLYURETHANE COATINGS

7.1 Abstract
Three non-isocyanate urethane dimethacrylates (NUDMA) reactive diluents were
synthesized by the reaction of the cyclic carbonate with the amino alcohol followed by
the reaction with the methacrylic anhydride. These NUDMA reactive diluents were
formulated with acrylated polyester (APE) oligomer to prepare UV-curable polyurethane
coatings. For comparison, ethylene glycol dimethacrylate (EGDMA) was also used as
reactive diluents. After UV curing, the viscoelastic, tensile and thermal properties of the
cured films were evaluated as a function of the reactive diluent by using dynamic
mechanical thermal analysis (DMTA), tensile test, differential scanning calorimeters
(DSC), and thermal gravimetric analysis (TGA). In addition, coating properties such as
pencil hardness, chemical resistance, impact resistance, and gloss were also investigated.
It was found that crosslink density, storage and tensile modulus, pencil hardness,
chemical resistance, gel content, total water absorption, and Tg were directly proportional
to amount of the reactive diluents. The NUDMA reactive diluents show significant
improvements in impact resistance and elongation at break properties compared to
136

EGDMA. It was found that the optimum level of the NUDMA reactive diluents
concentration is between 10-20 wt %.
7.2 Introduction
In recent years, UV-curable coating has received considerable increasing attention
because it is environmentally benign, fast curing, and lower energy consumption.
168
UV-
curable resin usually consists of three major components: photoinitiator, oligomer, and
reactive diluent.
194
The photoinitiator starts the photopolymerization when the resin
system is exposed to UV light. The oligomer photopolymerizes to form crosslinked film
and the structure of the oligomer governs viscoelastic properties of the final cured film.
The reactive diluent lowers the viscosity of the resin, and copolymerizes with oligomer
chemically bound into the final crosslinked film.
156

The photoinitiator for free radical polymerization usually contains aryl ketone
chemical structure shown in Figure 7- 1, which has strong UV light absorption in the
range of 200- 400 nm to produce free radicals. The structure of R
1
substituent influences
the absorption wavelength number; while the structure of R
2
substituent influences the
photoinitiator decomposition mechanism by scission process (unimolecular photoinitiator)
or abstraction process (bimolecular photoinitiator). The alkyl R
2
substituent will lead to
the scission process due to the relatively low bond energy of CO-alkyl; while the aryl R
2
substituent will lead to the abstraction process due to the relatively high bond energy of
CO-aryl. After absorbing UV light, the CO-aryl bond cannot be broken but remains the
excited state until it abstracts hydrogen from the hydrogen donor usually provided by
tertiary amine.
195

137

R
2
O
R
1

Figure 7- 1 The aryl ketone chemical structure
There are three major types of oligomers widely used in UV-curable coatings:
epoxy acrylate, polyester acrylate (acrylated polyester, APE), and urethane acrylate. The
most widely used epoxy acrylate is bisphenol A (BPA) acrylate oligomer. The
advantages of such epoxy acrylate include low cost, good adhesion, hardness, chemical
and solvent resistance
196
. This makes epoxy acrylate suitable for a wide variety of
applications, ranging from wood coatings for furniture and parquet flooring to disk
coatings and optical fiber coatings. The drawbacks of such epoxy acrylate include high
viscosity, low flexibility, and yellowing. This makes epoxy acrylate less suitable for
application on flexible substrates, low viscosity application techniques such spray and dip
coating, and outdoor applications.
The second type of oligomer is polyester acrylate (or acrylated polyester, APE)
oligomer; Polyester acrylates are usually prepared via the reaction of either the hydroxyl
terminated polyesters with acrylic acid or the carboxyl terminated polyesters with
hydroxyethyl acrylate. Acrylated polyesters have been studied in Souceks group.
194, 197,
125, 181
The advantage of acrylated polyesters is their versatile chemistry. Acrylated
polyester with varieties of functionality, chemical backbone and molecular weight could
be prepared by tailoring the starting monomers. Compared with epoxy acrylate, acrylate
polyester usually shows relatively lower hardness property. Its hardness and abrasion
resistance could be increased by incorporation of the tetraethylorthosilicate (TEOS)
oligomers to prepare inorganic/organic hybrid.
194, 197

138

The third type of oligomer is urethane acrylate oligomer. Urethane acrylate is
usually prepared by the reaction of a polyol with a diisocyanate to yield an isocyanate
terminated oligomer. These oligomers are then reacted with a hydroxyethyl acrylate
monomer.
171
Urethane acrylate is widely used as oligomer for UV coatings since it
provides excellent physical and mechanical properties such as high impact and tensile
strength, abrasion resistance and toughness combined with excellent resistance to
chemicals and solvents.
168, 171, 198, 170, 172, 173
Drawback of the urethane acrylate is the
toxicity of the isocyanate starting material.
199

The reactive diluents are usually acrylic or methacrylic monomers which are
added to reduce the viscosity of precured liquid oligomer and modify the property of final
cured solid film.
200
Generally mono-functional reactive diluents lead to decreased
modulus and increased ductility, whereas di- and multi- functional reactive diluents lead
to the opposite.
201
It was well established that high degree of functionality leads to high
reaction rates and high degree of crosslink density,
202
but also leads to reduced final
degree of conversion, because of early gelation of the irradiated sample and related
mobility restrictions of the reactive sites. In addition, the greater crosslink density leads
to glassy polymer materials, which are harder but also less flexible than monofunctional
type systems.
187, 163
The effect of monomer structure on oxygen inhibition of
(meth)acrylates photopolymerization were investigated. Compared to acrylates,
methacrylates are much less sensitive to oxygen.
203
The effect of the chemical structure
and functionality of the reactive diluents (ethylhexylacrylate, hexanediol diacrylate, and
isobornyl acrylate as reactive diluents) on the thermal and mechanical properties of the
UV-curable urethane acrylate oligomer were investigated. The functionality of the
139

reactive diluent does not affect the onset value of the glass transition temperature, but the
increase of the amount of the diacrylate monomer reactive diluent leads to an increase in
the equilibrium and storage modulus in the rubbery state.
204

One of the main goals in UV-curable coatings is to create new reactive diluents
that undergo fast and extensive polymerization to give final coatings having the desired
properties. Very promising results have been obtained by introducing acrylate monomer
(Acticryl CL-960) containing a urethane group into a UV-curable polyphenoxyacrylate
formulation. This urethane acrylate reactive diluent has distinct advantage of imparting
both hardness and elasticity to the cured films.
187
Recently, urethane dimethacrylate
monomer prepared via the non-isocyanate route from the reaction of a urethane diol with
methacrylic anhydride has been reported.
174, 175, 205
Photopolymerization of the urethane
dimethacrylate monomer was investigated with respect to polymerization rates and
conversions using photoinitiated differential scanning calorimetry.
174
The urethane
dimethacrylates as reactive diluents formulated with other acrylated oligomer to prepare
UV-curable coatings has never been reported. Previously, it has been reported that the
addition of the urethane diol into the high solid coating system can increase the
application solids and hardness.
199
Herein, it is expected that the addition of the urethane
dimethacylate into the UV-curable coating system could also increase mechanical
properties.
In this chapter, UV-curable polyurethane (PU) coatings were prepared by using
acrylated polyester (APE) as oligomer, and non-isocyanate urethane dimethacrylate
(NUDMA) as reactive diluents. The UV-curable PU coating prepared by this method
shows more environmental friendly compared with conventional UV-curable PU coatings
140

which consists of urethane acrylate oligomer and (meth)acrylate reactive diluents, and
increased mechanical property compared with UV-curable acrylated polyester coating
which consists of acrylated polyester oligomer and (meth)acrylate reactive diluents. As to
our knowledge, it is the first time to make UV-curable PU coating by using acrylated
polyester (APE) as oligomer, and non-isocyanate urethane dimethacrylate (NUDMA) as
reactive diluents.
7.3 Materials
Adipic Acid (AA), isophthalic acid (IPA), 1, 6 hexane diol (HD),
trimethylolpropane (TMP), p-xylene, dibutyl tin oxide (DBTO), ethylene carbonate (EC),
propylene carbonate (PC), 2-aminoethanol (EOA), 3-aminopropanol (POA), methacrylic
anhydride (MAA, 94%), dichloromethane, hydroquinone, Triethylene diamine (TEA) all
Aldrich products were used as received. 4-(dimethyl-amino)pyridine (DMAP) was
obtained from Acros Organics. Photoinitiator Darocur 4265 was obtained from Ciba
Specialty Chemical, NY. Aluminum panels (type A, alloy) (36 in) panels were obtained
from Q-panel Lab Products.
7.4 Instrumentation
The NMR spectra were taken in a Varian Mercury 300 MHz spectrophotometer.
Molecular weight and its distribution were determined by GPC (Waters Corporation).
The coating was cured by a Fusion UV-curing chamber (F300SQ Series) having a
mercury arc bulb (150 mW cm
-2
, UVB, 257 nm). Tensile and release tests were
performed on an Instron 5567 (Instron Corp., Grove City, PA). The viscoelastic
properties were measured on a dynamic mechanical thermal analyzer (DMTA, Q800, TA
141

Instruments). The thermo properties were characterized by differential scanning
calorimeters (DSC, Q200, TA Instruments) and thermogravimetric analysis (TGA, Q50,
TA Instruments).
7.5 Synthesis
In this synthesis part, acrylated polyester oligomer was synthesized by using two-
step reactions. Non-isocyanate urethane dimethacrylate reactive diluents were also
prepared by using two-step reactions.
7.5.1 Synthesis of the acrylated polyester (APE) oligomer
A typical poly-condensation technique was used to prepare APE oligomer
181
. The
synthesis process consists of two steps. In the first step, hydroxyl terminated polyester
polyol was prepared by using excess diol. The molar ratio of alcohol to acid is 11:8.
Adpic acid (AA) (100 g, 0.68 mol), isophthalic acid (IPA) (113.67 g, 0.68 mol), 1,6
hexane diol (HD) (161.71 g, 1.37 mol) and trimethylolpropane (TMP) (45.90 g, 0.34 mol)
were taken in a 500 ml four-neck round bottom flask which was equipped with a
mechanical stirrer, a gas inlet, a temperature controller, a Dean-Stark trap and a
condenser. The reaction proceeded under argon to minimize oxidative degradation. To
accelerate the reaction, 0.4 wt % of DBTO, a transesterification catalyst, was used. Then,
3 wt % of p-xylene was also added into the reaction mixture to remove water from the
resin as azeotropic mixture. The reaction temperature was carefully controlled using a
temperature controller and a thermocouple in order to minimize evaporation of diol. The
temperature of the mixture was increased from 20-150
o
C at a rate of 4.3
o
C /min, and
then from 150-210
o
C at a rate of 0.25
o
C/min. The final temperature was held until the
142

resin had an acid number measured by titration less than or equal to 10 mg KOH/g resin.
The hydroxyl number of polyesters (160.4 mg KOH/g resin) was determined by ASTM
method (ASTM D 1957-86). In the second step, the temperature was reduced to 120
o
C.
Acrylic acid (AA, the mole ratio of the acid in the AA to the hydroxyl in the polyester
polyol kept at 1.05), 1 wt % p-toluene sulphonic acid (p-TSA, catalyst) and 0.05 wt %
hydroquinone (inhibitor) (based on the total amount of the polyester polyol and acrylic
acid) were added in, the temperature was maintained at 120
o
C for 14h. Then, 1.5 wt % of
3- methyl-3-hydroxymethyl-oxetane was added in, and maintained at 120
o
C for another
20 min. Then solvent and residual were removed in vacuo resulting in a light yellow
acrylated polyester oligomer.
1
H NMR (300 MHz, CHLOROFORM-d) (ppm) 0.84 -
0.98 (m, 2 H) 1.33 - 1.47 (m, 8 H) 1.50 - 1.53 (m, 1 H) 1.56 - 1.69 (m, 11 H) 1.73 - 1.83
(m, 4 H) 2.22 -2.39 (m, 6 H) 3.57 - 3.69 (m, 1 H) 3.99 - 4.16 (m, 6 H) 4.27 - 4.44 (m, 5 H)
5.75 - 5.89 (m, 1 H) 6.03 - 6.16 (m, 1 H) 6.32 - 6.44 (m, 1 H) 7.45 - 7.56 (m, 1 H) 8.11 -
8.28 (m, 2 H). The average molecular weight was found to be Mn = 3500, with a PDI =
1.8 via GPC.
7.5.2 Synthesis of non-isocyanate urethane dimethacrylate reactive diluents
The synthesis process consists of two steps. In a typical procedure to prepare
EOAED, In the first step, urethane diol (EOA-EC) was prepared by modification of the
Rokickis procedure.
178
Ethylene carbonate (88.06 g, 1.00 mol) was dissolved in 100 mL
dichloromethane, and such solution was drop added into the 2-aminoethanol (61.08 g,
1.00 mol) and dichloromethane (200 mL) mixture at 0
o
C. After finish adding, the mixture
was stirred at room temperature for 24 hour. The slightly yellow liquid (yield: 98%) was
got by rot vaporing the dichloromethane. In the second step, urethane dimethacrylate was
143

prepared by modification of Assumptions procedure.
174
Urethane diol EOA-EC (14.9 g,
0.1 mol) was dissolved in 300 mL dichloromethane at 0
o
C, 4-(dimethyl-amino)pyridine
(DMAP) catalyst (122 mg, 1 mmol), and 0.05 wt % hydroquinone (inhibitor) (28 mg)
were added in, followed by drop addition of triethylene diamine (TEA) (28.3 g, 0.28 mol),
and then drop addition of methacrylic anhydride (39.4g, 0.24 mol) under the N
2

atmosphere. The reaction mixture was stirred at 0
o
C for 24 hours. Then saturated sodium
bicarbonate solution (294.7g) was dropped added to get two phase separated mixture. The
product (top layer) was collected, washed with brine (300 ml 3) and water (300 ml 2),
and dried in anhydrous magnesium sulphate. After dichloromethane was evaporated, the
final liquid product with pale yellow color was got (yield: 42%).
1
H NMR (300 MHz,
DMSO-d
6
) (ppm) = 1.86(m, 6 H, -CH
3
), 3.27 (qd, J = 5.67, 1.39 Hz, 2 H, -CH
2
NH-),
4.07 (td, J=5.57, 1.63 Hz, 2 H,-OCH
2
CH
2
O-), 4.12 (m, 2 H, -OCH
2
CH
2
NH-), 4.14 - 4.30
(m, 2 H,-OCH
2
CH
2
O-), 5.62 - 5.78 (m, 2 H, trans C=CH
2
) 5.98 - 6.12 (m, 2 H, cis
C=CH
2
), 7.42(t, 1 H, -NHCOO-).
13
C NMR (300 MHz, DMSO-d
6
) (ppm) 18.11 (-CH
3
),
39.79 (-CH
2
NH-), 62.11 (-NHCOOCH
2
-), 63.32 (-CH
2
CH
2
O-), 63.49 (-COOCH
2
-),
126.18 (C=CH
2
), 136.10 (C=CH
2
), 156.46 (C=O, carbamate), 166.67 (C=O, ester).
Figure 7- 2 summarizes the urethane dimethacrylate prepared by this method.
144

O
H
N O
O
O O
O
O
H
N O
O
O O
O
POAED
POAPD
O
H
N O
O
O O
O
O
O N
H
O
O
O
O
EOAED
O
O
O
O
EGDMA

Figure 7- 2 Reactive diluents chemical structure
7.6 Coating formulation and evaluation
Aluminum and glass panels were used as the substrate for film preparation. The
substrates were cleaned with distilled water and acetone and dried. The formulations
were made by taking specific amount of synthesized non-isocyanate urethane
dimethacrylate reactive diluent EOAED, POAED, POAPD, or dimethacrylate EGDMA
145

and mixing them with specific amount of synthesized APE oligomer and 2 wt% (based
on the total resin) photoinitator Darocur 4265 in a glass vial at room temperature
thoroughly for 20 min. The formulations are shown in Table 7- 1. The films were cast on
either aluminum or glass substrates with a thickness of 150 m (6 mil) by a drawdown
bar. The films were UV cured using a Fusion UV System processor (P300) at the belt
speed of 5 fpm and stored in a dust free cabinet for testing purposes.
Table 7- 1 The formulation of non-isocyanate PU with different reactive diluents at
different concentration
Sample

APE oligomer
(wt %
a
)
Reactive Diluent
(wt %)
Photoinitiator
(wt %)
APE 100 0 2
RD
b
-10 90 10 2
RD-20 80 20 2
RD-30 70 30 2
RD-40 60 40 2
a. Photoinitiator weight percentage (wt%) is based on the total weight of oligomer
and reactive diluents
b. RD means EGDMA, EOAED, POAED, and POAPD in specific case
Coating properties were evaluated according to ASTM methods including pencil
hardness (D3363-05), impact resistance (G14), gloss rating (D523-89), and MEK double
rubs (D4752-06). The gel content of the cured coating films was determined by Soxhlet
extraction using acetone for 48 h.
206, 207
The insoluble gel fraction was dried under
vacuum for 24 h at 60
o
C and weighed to determine the gel content. To measure the water
absorption of a crosslinked coating, around 0.2 g coating sample was dried in vacuum for
24 h at 100
o
C, and then dipped in water at room temperature for 72 h. Afterwards, the
wet sample without free water was weighed. The water absorption was then calculated
208

from the difference in the weights of the sample before and after soaking in the water
according to equation 7-1.
146

(7-1)
where wt
after
is the weight of the sample after dipping in the water, and wt
before
is
the weight of the sample before dipping in the water.
7.7 Results
The overall objective of was to prepare a UV-curable non-isocyanate PU coating,
The UV-curable non-isocyanate PU coating consists of acrylated polyester as oligomer,
non-isocyanate urethane dimethacrylate as reactive diluent and Darocur 4265 as free
radical photoinitiator. In this study, we focused on the non-isocyanate urethane
dimethacrylate (NUDMA) reactive diluents. The NUDMA was prepared from the
reaction of urethane diol and methacrylic anhydride. The liquid urethane diol was
synthesized from the reaction of amino alcohol with cyclic carbonate via non-isocyanate
route shown in Figure 6- 2. It is of interest to study the effect of the NUDMA reactive
diluents on the coating properties, and compare NUDMA with conventional EGDMA.
To investigate the effect of the NUDMA reactive diluents on the coating
properties, and compare NUDMA with conventional EGDMA reactive diluent, coatings
containing different reactive diluents and concentration were prepared; the formulation
was shown in Table 7-1. After UV curing, the general coating properties (hardness, gloss,
MEK rub resistance and impact resistance) of non-isocyanate polyurethane coating were
measured to evaluate effects of the urethane group on the film properties. The thermal
and mechanical properties of the cured films were obtained using DSC, TGA and tensile
test, respectively. The viscoelastic properties of the coating were investigated using
DMTA. The glass transition temperature (T
g
) and crosslink density of the coatings were
147

derived from the tan and storage moduli (E), respectively. In addition, water
absorption and gel content properties of the films were also investigated.
7.7.1 Tensile properties
The tensile strength, elongation at break, and tensile modulus as a function of
reactive diluents content are shown in Figure 7- 3, and summarized in Table 7- 2. The
tensile strength is increased with the addition of any each of these four reactive diluents.
When EGDMA is used as the reactive diluent, the tensile strength shows a large increase
from 1.99 MPa at 0 wt % to 6.19 MPa at 10 wt % till 13.36 MPa at 20 wt % EGDMA
reactive diluents content, and a minor increase from 13.36 MPa at 20 wt % to maximum
of 14.5 MPa at 30 wt % EGDMA reactive diluents content. The tensile strength is
decreased to 9.78 MPa at 40 wt % EGDMA reactive diluents content. When EOAED or
POAPD is used as the reactive diluent, the tensile strength shows a continuous increase
with the amount of reactive diluent, and reaches the maximum at 40 wt % reactive
diluents content. The maximum tensile strength of EOAED system is 29.51 MPa, which
is 2.1 times higher than the EGDMA system; and the maximum tensile strength of
POAPD system is 26.30 MPa, which is 1.8 times higher than the EGDMA system. When
POAED is used as the reactive diluent, the tensile strength shows increase with the
amount of reactive diluent initially, and reaches the maximum at 30 wt % reactive
diluents content. The maximum tensile strength of POAED system is 21.96 MPa, which
is 1.5 times higher than the EGDMA system.
For EGDMA system, the elongation at break is decreased with the addition of
reactive diluents. The elongation at break shows a continuous decrease from 20.64 % at
0 wt % to the minimum of 1.26 % at 40 wt % EGDMA reactive diluents content. For all
148

these three NUDMA systems, the elongation at break increased from 20.64 % to 27.95 %
(EOAED system), 27.19 % (POAED system) and 25.56 % (POAPD system) with the
addition of 10 wt % reactive diluents, separately. The elongation at break of these three
NUDMA systems remained constant as the reactive diluents increased to 20 wt % (within
experimental error). After which, the elongation at break decreased as the reactive
diluents increased from 20 wt % to 40 wt %. As comparing of the NUDMA system with
the EGDMA system, the elongation at break of these three NUDMA systems is always
higher than that of the EGDMA system at the same percent loading in the range of 10
40 wt %. The elongation at break of these three NUDMA systems is around 1.6-1.7 times
higher than that of the EGDMA system at 10 wt % loading, 2.8-2.9 times higher at 20 wt %
loading, 3.0-4.8 higher at 30 wt % loading, and 2.2-5.0 times higher at 40 wt % loading.
The tensile modulus shows a continuous increase with the addition of any each of
these four reactive diluents in the percent loading range of 10-40 wt %. At 10 wt %
loading of reactive diluents, the tensile modules increased from 12.60 MPa to 48.62 MPa
for EGDMA system, and to around 23 MPa for the three NUDMA system; as the percent
loading is increased from 10 -20 wt %, the tensile modulus increased to 212 MPa for
EGDMA system, and to around 87 MPa for the three NUDMA system; as the percent
loading is increased from 20 -30 wt %, the tensile modulus increased to 524 MPa for
EGDMA system, and to around 345 MPa for the three NUDMA system; as the percent
loading is increased from 30 -40 wt %, the tensile modulus increased to 968 MPa for
EGDMA system, and to around 974 MPa for the three NUDMA system. The tensile
modules of the EGDMA systems is around 2 times higher than that of the NUDMA
149

system in the percent loading range of 10-20 wt %, 1.5 times higher at 30 wt % loading,
and almost equal at 40 wt % loading.
APE EGDMA EOAED POAED POAPD --
0
10
20
30
40



T
e
n
s
i
l
e

S
t
r
e
s
s

(
M
P
a
)
0
10
20
30
40
a.
APE EGDMA EOAED POAED POAPD --
0
5
10
15
20
25
30
35



E
l
o
n
g
a
t
i
o
n

a
t

B
r
e
a
k

(
%
)
0
10
20
30
40
b.

APE EGDMA EOAED POAED POAPD
0
200
400
600
800
1000
1200
1400



M
o
d
u
l
u
s

(
M
P
a
)
0
10
20
30
40
c.

Figure 7- 3 Tensile properties of UV cured coating as a function of reactive diluents: (a)
tensile strength; (b) elongation at break; (c) tensile modulus







150

Table 7- 2 Tensile properties of UV cured coating as a function of reactive diluents type
and content
Samples Modulus
Elongation at
break Tensile stress

(MPa) (%) (MPa)

APE 12.60 0.60 20.64 0.93 1.99 0.09

EGDMA-10 48.62 3.63 15.83 1.40 6.19 0.22
EGDMA-20 212.10 13.38 9.77 0.44 13.36 0.84
EGDMA-30 523.79 100.16 3.76 0.98 14.05 2.62
EGDMA-40 968.31 238.84 1.26 0.30 9.78 3.34

EOAED-10 21.49 0.82 27.95 1.49 4.98 0.31
EOAED-20 89.20 3.49 28.37 2.76 15.88 1.68
EOAED-30 348.70 31.13 13.60 0.43 20.55 2.02
EOAED-40 1010.93 139.55 4.71 0.43 29.51 3.80

POAED-10 26.14 1.92 27.19 1.16 5.91 0.28
POAED-20 97.50 3.68 26.91 1.21 16.11 0.99
POAED-30 428.42 84.37 11.33 2.34 21.96 1.34
POAED-40 1114.39 46.87 2.72 1.01 21.53 6.56

POAPD-10 22.36 2.38 25.56 2.08 4.29 0.35
POAPD-20 73.65 7.17 22.23 2.03 10.75 0.36
POAPD-30 258.00 31.20 18.00 2.75 20.46 1.77
POAPD-40 796.94 54.08 6.30 1.64 26.30 3.42

7.7.2 Viscoelastic properties
The viscoelastic properties of the UV cured coating films were investigated using
DMTA. An example of the DMTA data, depicting storage modulus (E), loss modulus
(E), and tan, is shown in Figure 7- 4.
151

-80 -40 0 40 80 120 160 200 240
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
E'
E''

E
'

(
M
P
a
)

a
n
d

E
'
'

(
M
P
a
)
Temperature (
o
C)
0.0
0.2
0.4
0.6
0.8
1.0
T
a
n

D
e
l
t
a

Tan Delta

Figure 7- 4 Dynamic mechanical properties of APE coating system. E storage
modulus; E, loss modulus; tan = E/E

The storage modulus (E) remained almost constant as the temperature was
increased up to the glass transition and started to decrease during the transition. The
decrease reached a minimum value and then slightly increased with temperature forming
a rubbery plateau as described in equation 7-2.
146

E = 3
e
RT (T >> Tg) (7-2)
Where
e
is the number of moles of elastically effective network chains per cubic
meter of film and E is tensile storage modulus. This relationship is effective when
T >>Tg, and for low crosslink density elastomers. For the highly crosslinked system, it
can only be used to evaluate the relative density of crosslinking. Crosslink density was
152

calculated by this equation with the E at corresponding temperature T (T > Tg + 50).
The minimum of storage modulus, E(min), was recorded as the minimum value in
rubbery plateau. The Tg was obtained from the maximum of the -transition. The Tg,
minimum elastic modulus (E), crosslink density (
e
), breadth of tan transition, and
maximum tan transition as a function of reactive diluents are summarized in Table 7- 3.
Table 7- 3 Viscoelastic properties of UV cured coating as a function of reactive diluents
type and content

T for E'
min

(
o
C)
E'
min

(MPa)

e

(mol/m
3
)
Tg
(
o
C)
Tan
Breadth (
o
C)
Max.
Tan
APE 91.17 4.92 541.66 43.10 24.99 0.91
EGDMA-10 179.48 12.33 1092.17 47.52 48.61 0.39
EGDMA-20 227.53 42.32 3388.86 52.21 71.66 0.25
EGDMA-30 239.61 63.26 4946.34 59.88 98.95 0.18
EGDMA-40 240.00 167.20 13063.53 61.59 123.19 0.13
EOAED-10 115.03 11.49 1186.74 55.41 45.28 0.48
EOAED-20 214.49 13.48 1108.31 61.80 68.38 0.36
EOAED-30 220.42 15.82 1285.07 75.45 101.64 0.27
EOAED-40 227.42 22.83 1828.56 127.83 131.21 0.23
POAED-10 134.53 12.33 1212.59 54.34 49.89 0.45
POAED-20 190.27 14.54 1257.94 61.16 74.85 0.32
POAED-30 232.40 25.09 1989.78 72.68 98.86 0.24
POAED-40 230.40 29.21 2325.72 97.41 123.82 0.20
POAPD-10 122.94 12.30 1245.03 53.91 39.74 0.59
POAPD-20 160.75 17.84 1648.44 69.69 64.68 0.38
POAPD-30 179.33 25.02 2216.95 79.92 86.86 0.29
POAPD-40 196.58 25.40 2167.97 103.81 116.43 0.24

The storage modulus E as a function of different reactive diluents of EGDMA,
EOAED, POAED, and POAPD are shown in Figure 7- 5. E(min) and the crosslink
density (
e
) of the cured films increased with addition of the all four reactive diluents. At
10 wt % reactive diluents load, the storage modulus was doubled with the addition of the
each of the four reactive diluents. The storage modulus was increased from 4.92 MPa to
12.33 MPa for EGDMA system, 11.49 MPa for EOAED system, 12.33 MPa for POAED
153

system and 12.30 MPa for POAPD system. As comparing of the NUDMA system with
the EGDMA system, the storage modulus of these three NUDMA systems is always
lower than that of the EGDMA system at the same percent loading in the range of 20 40
wt %. Crosslink density (
e
) of these four cured films exhibits the same trends as storage
modulus.
-80 -40 0 40 80 120 160 200 240
10
1
10
2
10
3
10
4
EGDMA-40
EGDMA-30
EGDMA-20
EGDMA-10

E
'

(
M
P
a
)
Temperature (
o
C)
a.
-80 -40 0 40 80 120 160 200 240
10
1
10
2
10
3
10
4
EOAED-40
EOAED-30
EOAED-20
EOAED-10

E
'

(
M
P
a
)

Temperature (
o
C)
b.

-80 -40 0 40 80 120 160 200 240
10
1
10
2
10
3
10
4
POAED-40
POAED-30
POAED-20
POAED-10

E
'

(
M
P
a
)
Temperature (
o
C)
c.
-80 -40 0 40 80 120 160 200 240
10
1
10
2
10
3
10
4
POAPD-40
POAPD-30
POAPD-20
POAPD-10

E
'

(
M
P
a
)
Temperature (
o
C)
d.

Figure 7- 5 Modulus (E) as a function of temperature of the UV curable coating with
different reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d) POAPD
The tan as a function of different reactive diluents of DGEMA, EOAED,
POAED, and POAPD are shown in Figure 7- 6. Tg and breadth of tan transition of the
cured films increased with addition of the all the four reactive diluents. The maximum of
tan transition of the cured films decreased with addition of the all the four reactive
154

diluents. At the same percent loading in the range of 10 40 wt %, Tg and maximum of
tan transition of all three NUDMA system is higher than that of the EGDMA system,
and breadth of tan transition of all four cured films shows similar values with each other.
-80 -40 0 40 80 120 160 200 240
0.0
0.1
0.2
0.3
0.4
0.5

T
a
n

D
e
l
t
a
EGDMA-40
EGDMA-30
EGDMA-20
EGDMA-10

Temperature (
o
C)
a.
-80 -40 0 40 80 120 160 200 240
0.0
0.1
0.2
0.3
0.4
0.5
0.6

T
a
n

D
e
l
t
a
EOAED-40
EOAED-30
EOAED-20
EOAED-10

Temperature (
o
C)
b.

-80 -40 0 40 80 120 160 200 240
0.0
0.1
0.2
0.3
0.4
0.5
0.6

T
a
n

D
e
l
t
a
POAED-40
POAED-30
POAED-20
POAED-10

Temperature (
o
C)
c.
-80 -40 0 40 80 120 160 200 240
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7

T
a
n

D
e
l
t
a
POAPD-40
POAPD-30
POAPD-20
POAPD-10

Temperature (
o
C)
d.

Figure 7- 6 Tan as a function of temperature of the UV curable coating with different
reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d) POAPD
7.7.3 Thermal properties
The thermal properties of the UV cured coatings were further investigated using
DSC and thermal gravimetric analysis (TGA). The DSC thermograms as a function of
reactive diluents are shown in Figure 7- 7. The corresponding Tg and Cp derived from
the DSC data are summarized in the Table 7- 4.
155

-100 -50 0 50 100 150


H
e
a
t

F
l
o
w

(
W
/
g
)
,

E
x
o

U
p
Temperature (
o
C)
APE
EGDMA-10
EGDMA-20
EGDMA-30
EGDMA-40
a.
-100 -50 0 50 100 150


H
e
a
t

F
l
o
w

(
W
/
g
)
,

E
x
o

U
p
Temperature (
o
C)
APE
EOAED-10
EOAED-20
EOAED-30
EOAED-40
b.

-100 -50 0 50 100 150


H
e
a
t

F
l
o
w

(
W
/
g
)
,

E
x
o

U
p
Temperature (
o
C)
APE
POAED-10
POAED-20
POAED-30
POAED-40
c.
-100 -50 0 50 100 150


H
e
a
t

F
l
o
w

(
W
/
g
)
,

E
x
o

U
p
Temperature (
o
C)
APE
POAPD-10
POAPD-20
POAPD-30
POAPD-40
d.

Figure 7- 7 DSC thermograms as a function of temperature of the UV curable coating
with different reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d)
POAPD










156

Table 7- 4 DSC data of UV cured coating as a function of reactive diluents type and
content
Samples Tg (C)
Delta Cp
(J/(gC))
APE -18.01 0.53
EGDMA-10 -12.40 0.43
EGDMA-20 -13.06 0.40
EGDMA-30 -13.15 0.36
EGDMA-40 -13.05 0.29
EOAED-10 -9.88 0.51
EOAED-20 -4.22 0.42
EOAED-30 1.09 0.40
EOAED-40 3.43 0.27
POAED-10 -10.63 0.49
POAED-20 -9.22 0.45
POAED-30 -3.80 0.30
POAED-40 -2.87 0.25
POAPD-10 -10.33 0.54
POAPD-20 -9.42 0.51
POAPD-30 -6.88 0.51
POAPD-40 2.33 0.34

For EGDMA system, the Tg increased with initial addition of 10 wt % reactive
diluent, and kept at the same level with reactive diluent further increasing to the load
range of 20-40 wt%. For all three NUDMA systems, the Tg kept continuously increasing
with the addition of the reactive diluents in the load range of 10-40 wt%. For all the four
systems, the Cp decreased with the addition of the reactive diluents. As a comparison,
the Tg of the NUDMA system is always higher than that of the EGDMA system at the
same reactive diluents content.
Thermal gravimetric analysis (TGA) was used in this study to evaluate the
thermal decomposition of these UV cured coatings as a function of reactive diluent type
157

and content. Representative dynamic TGA curves for UV cured coatings with various
compositions are shown in Figure 7- 8. The TGA data are summarized in Table 7- 5.
0 100 200 300 400 500 600
0
20
40
60
80
100
APE
EGDMA-10
EGDMA-20
EGDMA-30
EGDMA-40


W
e
i
g
h
t

(
%
)
Temperature (
o
C)
a.
0 100 200 300 400 500 600
0
20
40
60
80
100
APE
EOAED-10
EOAED-20
EOAED-30
EOAED-40


W
e
i
g
h
t

(
%
)
Temperature (
o
C)
b.

0 100 200 300 400 500 600
0
20
40
60
80
100
APE
POAED-10
POAED-20
POAED-30
POAED-40


W
e
i
g
h
t

(
%
)
Temperature (
o
C)
0 100 200 300 400 500 600
0
20
40
60
80
100
APE
POAPD-10
POAPD-20
POAPD-30
POAPD-40


W
e
i
g
h
t

(
%
)
Temperature (
o
C)
d.

Figure 7- 8 TGA thermograms as a function of temperature of the UV curable coating
with different reactive diluents of (a) EGDMA; (b) EOAED; (c) POAED; and (d)
POAPD








158

Table 7- 5Thermogravimetric Analysis (TGA) data of UV cured coating as a function of
reactive diluents type and content
Sample
Temperature (C) required to produce % weight loss
5% 10% 25% 50%
APE 307 348 374 401

EGDMA-10 319 351 382 406
EGDMA-20 314 347 378 403
EGDMA-30 313 345 378 404
EGDMA-40 316 347 379 406

EOAED-10 291 330 371 398
EOAED-20 279 319 370 399
EOAED-30 270 313 367 399
EOAED-40 256 303 357 396

POAED-10 298 336 375 402
POAED-20 295 331 376 404
POAED-30 290 326 374 405
POAED-40 279 319 367 402

POAPD-10 291 334 375 402
POAPD-20 279 323 371 400
POAPD-30 262 313 365 398
POAPD-40 251 305 358 396

For the most part, reactive diluent concentration had no major impact on the films
thermal stability until higher temperatures (>300
o
C) were achieved
149
. Figure 7- 8a shows
the TGA data for EGDMA systems. It was found that the sample degradation of 5% took
place at 307
o
C for neat polyester coating, between 313-319
o
C for coating containing 10-
40 wt. % EGDMA reactive diluent. It indicated that the thermal stability of the UV cured
polyester coatings was slightly increased with the addition of the EGDMA reactive
diluent. Figure 7- 8b shows the TGA data for EOAED systems. It was found that there
was a shift to slightly lower temperatures as the EOAED reactive diluent loading
159

increased. The sample degradation of 5% took place at 291
o
C with 10 wt % reactive
diluent content, at 279
o
C with 20 wt% reactive diluent, at 270
o
C with 30 wt% reactive
diluent, and at 256
o
C with 40 wt% reactive diluent. It indicated that the thermal stability
of the UV cured polyester coatings was kept decreasing with the addition of the EOAED
reactive diluent. The other POAED and POAPD system exhibit similar trends as EOAED
system. The shapes of the weight loss curves of all NUDMA system are almost identical,
and overall differences in thermal stability appear to be small.
7.7.4 Gel content properties
In order to further investigate the crosslink properties of the cured coating films,
the gel content measurements were performed. The gel content as a function of the
different reactive diluents is shown in Figure 7- 9. The gel contents of the cured films
increased with addition of all the four reactive diluents, and show similar values at the
same percent loading in the range of 10 40 wt %. For all of these four cured coating
films, the gel contents were increased from 88% initiately to 90% at 10 wt %, to 91 % at
20 wt %, to 92% at 30 wt %, and to 93% at 40 wt % reactive diluents load.
160

0 10 20 30 40
87
88
89
90
91
92
93
94


EGDMA
EOAED
POAED
POAPD
G
e
l

C
o
n
t
e
n
t

(
W
t

%
)
Reactive Diluents Weight Percentage (Wt %)

Figure 7- 9 Effect of the reactive diluent type and content on the gel content properties of
UV cured coatings
7.7.5 Water absorption properties
The effect of the reactive diluents on cured film was further verified in terms of
water adsorption
209
. In Figure 7- 10, it is shown that the water absorption of the cured
films increased with addition of all the four reactive diluents, and the water absorption of
EGDMA system was found to be slightly lower than other three NUDMA system.
161

0 10 20 30 40
0.5
1.0
1.5
2.0
2.5
3.0
3.5


EGDMA
EOAED
POAED
POAPD
W
a
t
e
r

A
b
s
o
r
p
t
i
o
n

W
e
i
g
h
t

P
e
r
c
e
n
t
a
g
e

(
W
t

%
)
Reactive Diluents Weight Percentage (Wt %)

Figure 7- 10 Effect of the reactive diluent type and content on the water absorption
properties of UV cured coatings
7.7.6 General coating properties
A summary of the cured coating properties is found in Table 7- 6. After complete
UV curing, several film properties were evaluated: pencil hardness, impact resistance,
gloss, and solvent resistance. It was found that the pencil hardness did not change with
the addition of 10 wt% reactive diluents, and increased from 2B to HB with the addition
of 20-40 wt % reactive diluents for all systems. The impact resistance of the EGDMA
system was decreased with the addition of reactive diluents in the load range of 10-40
wt %. The impact resistance of the three NUDMA systems was increased with addition
162

of 10 -20 wt % reactive diluents, and decreased with addition of 30-40 wt % reactive
diluents. The methyl ethyl ketone (MEK) solvent resistance was increased with the
addition of reactive diluents in the load range of 10-40 wt % for all systems. It was found
that there was no effect on the gloss with the incorporation of the reactive diluents for all
systems.
Table 7- 6 General coating properties as a function of reactive diluents type and content
Samples
Direct
impact
(kg/cm)
Reverse
impact
(kg/cm)
Pencil
hardness
MEK
double
rubs
60
o
C
Gloss
20
o
C
Gloss
APE 64 56 2B 16 181 3 142 2

EGDMA-10 55 52 2B 20 187 4 148 7
EGDMA-20 50 40 HB 60 185 2 146 7
EGDMA-30 44 42 HB >200 184 4 144 7
EGDMA-40 26 7 HB >200 183 2 131 18

EOAED-10 92 87 2B 36 189 2 149 2
EOAED-20 90 71 HB 44 182 2 140 6
EOAED-30 56 43 HB >200 180 5 138 6
EOAED-40 30 8 HB >200 183 4 145 5

POAED-10 85 71 2B 22 185 1 147 5
POAED-20 77 71 HB 67 185 3 149 4
POAED-30 47 31 HB >200 182 1 140 4
POAED-40 31 10 HB >200 186 3 147 3

POAPD-10 88 82 2B 18 189 2 154 8
POAPD-20 86 84 HB 44 190 2 145 6
POAPD-30 61 58 HB >200 185 1 146 7
POAPD-40 39 11 HB >200 186 2 143 5

7.8 Discussion
Generally, the UV-curable PU coatings were formulated using the urethane
acrylate oligomers and (meth) acrylate reactive diluents. The urethane acrylate oligomer
163

was prepared from the reaction of a polyol with a diisocyanate followed by the reaction
with hydroxyl acrylate monomer
171
. The drawback of the urethane acrylate oligomer is
the use of the toxic isocyanate starting material. In this study, UV curable PU coating
were prepared by using acrylated polyester (APE) as oligomer, and non-isocyanate
urethane dimethacrylate (NUDMA) as reactive diluents. The UV curable PU coating
prepared by this new method shows more environmental friendly compared with
conventional UV curable PU coatings.
The tensile modulus of UV cured coating increased with the addition of the
reactive content. This result is attributed to intra/inters molecular reaction between APE
oligomer and reactive diluent, and the increase in crosslink density with the addition of
reactive diluents. The tensile modulus of the NUDMA system is lower than that of the
EGDMA system with the same content of reactive diluent, this may due to the fact that
NUDMA system provide lower crosslinking sites for the coatings. The trend in the
storage modulus mirrored the trend in tensile strength. The increase in tensile and storage
modulus as the concentration of reactive diluents increased corroborated the crosslink
density, Tg, impact resistance and gel content data. For EGDMA system, flexibility of
the film was reduced as measured by elongation at the moment of breakage. Such
reduction in elongation was expected due to higher concentration of joint site between
polymer chains, which restrict the polymer movement upon stretching
147
. More
interestingly for NUDMA system, the elongation at break increased with addition of the
10-20 wt% reactive diluent, and decreased with further increasing reactive diluent to 30-
40 wt%. Such behavior might be the results of increasing physical interaction forces from
the hydrogen bonding among urethane groups. The effect of the reactive diluent type and
164

content on the impact properties exhibits the similar trends as elongation at break
properties. That is another evidence of improvement of the flexibility achieved through
physical interaction forces via the hydrogen bonding in the NUDMA system.
The dynamic mechanical analysis of UV cured film with increasing reactive
diluent concentrations showed two major trends. One corresponded to broadening of the
transition region and the other represented the shift of the maximum tan value toward
lower numbers and higher temperatures. The breadth of a transition region is closely
related to the degree of heterogeneity.
125, 148
As given in Table 7- 3, tan transition
breadths was increased with the content of the reactive diluent, but independent of type of
the reactive diluent, which suggested that the extent of reactive diluent has major impact
on the heterogeneity, and higher amount of urethane group incorporation not necessarily
cause more heterogeneous systems. The crosslink density has a direct impact on the tan
such that it reduces long range segmental motion required for viscous flow behavior.
149

As a result, the maximum tan can be used to compare the extent of cure. The maximum
tan decreases as the extent of reactive diluents. This indicates that the crosslink density
of the UV cured films increases with reactive diluent content. The maximum tan of the
EGDMA system is lower than that of the NUDMA system at the same reactive diluent
content. This is another evidence to show that the EGDMA system has a higher crosslink
density, and higher tensile and storage modulus. The Tg was obtained as the maximum of
tan . It was found the Tg increased with the content of the reactive diluent, and the Tg of
NUDMA system is higher than that of the EGDMA system. On the molecular scale, the
glass transition temperature of a polymeric material is the temperature at which the
micro-Brownian movements of the molecular chain segments become significant.
165

Therefore, any responses of the material to a chemical and physical environment only
occurs at or above the glass transition temperature.
210
An increase in Tg corresponded to
a decrease in mobility in the polymer. The formation of the crosslinking networks
between the reactive diluent and acrylated polyester oligomers would hinder the
movement of the polymer chains, resulting in the increase of the Tg.
150
It indicates that
with the increase of reactive diluent content, the crosslink density of UV cured coating
enhanced, leading to the increase of Tg of the coating. The Tg of the NUDMA system is
higher than that of the EGDMA system. This can be attributed to the additional physical
crosslink density formation via the hydrogen bonds between the urethane groups in the
NUDMA system. As a comparison, the Tg measured by DSC exhibited the same trends
as the Tg measured by DMTA. But the Tg measured by DSC were lower than the Tg
measured by DMTA. This result can be due to a fact that the glass transition temperature
of a polymeric material is a kinetic parameter which is affected by the time scale of the
measurements.
210

The thermostability of UV cured coating is independent on the content of the
EGDMA reactive diluent, but decreased with the extent of the NUDMA reactive diluent.
This is attributed to the fact that the degradation process is caused by the dissociation of
the ester bond in the EGDMA system, and the degradation process is caused by the
dissociation of the urethane bond and ester bond in the NUDMA system. The urethane
bond was known to be relatively thermally unstable materials, and decomposition of the
urethane bond starts at about 150200C.
211
This suggests that degradation starts at the
urethane bond in the NUDMA system.
166

The gel is the portion of a material that does not dissolve in a solvent. Given a
proper solvent, the gel content is primarily determined by the molecular weight and the
geometry of the molecules. After crosslinking, the molecules of the coatings are formed
into a three dimensional network and the entropy of the molecules was reduced.
Consequently, the material dissolved less in the solvent and resulted in higher gel content.
Thus, the gel content is proportional to the crosslink density.
208
The gel contents of all the
cured films increased with addition of reactive diluents, this indicates that the crosslink
density increased with the addition of the reactive diluents.
The properties of water absorption by polymers have received considerable
attention, due to the importance of these phenomena in the case of environmental ageing
of polymers. Certain authors have found that the water absorption of polymers is directly
related with their free volume fraction,
212
while others have found that it is linked to the
presence of polar groups capable to form hydrogen bonds with water molecules, and
there is no apparently influence of the large-scale structure (crosslinking) of the polymer
on water absorption.
212-213
The water absorption of the cured films increased with the
content of reactive diluents. It could be attributed the fact that the increase of the reactive
diluent leads to the increase of the ester/urethane polar groups in the APE polymer matrix,
increasing the interaction of the APE polymer and water, resulting in the increase in the
total water absorption. It is known that the urethane group shows more polarity than the
ester group. This results in the higher total water absorption of the NUDMA systems
comparing with the EGDMA system.
Improvement of pencil hardness and MEK chemical resistance can be anticipated
with the amount of reactive diluents incorporated into the system. This can be attributed
167

to the increase in crosslink density of the UV cured films which reduced the flexibility of
the coating system. Similarly, the decrease in impact resistance with an increase in the
concentration of EGDMA can also be attributed to the increase in crosslink density. But
for NUDMA system, the increase in impact resistance with the addition of 10-20 wt %
reactive diluent, and decreased with further increasing reactive diluent to 30-40 wt%.
This phenomenon can be attributed to combined effects of two factors: the physical
interaction force via hydrogen bonds in the urethane groups and crosslink density. At the
low reactive diluent load, the physical interaction force via hydrogen bonds plays the
dominant role in the effect of the impact resistance which favors the improvement of the
impact resistance; while at the high reactive diluent load, the crosslink density factor
plays the dominant role in the effect of the impact resistance which leads to the decrease
in the impact resistance.
7.9 Conclusions
The new type and more environmental friendly UV curable polyurethane coatings
were formulated using the acrylated polyester (APE) as oligomer and non-isocyanate
urethane dimethacrylates (NUDMA) as reactive diluents. The UV-cured coatings
properties were dependent on the reactive diluents type and content. Crosslink density,
storage and tensile modulus, pencil hardness, chemical resistance, gel content, total water
absorption, and Tg were proportional to the content of the reactive diluents. Comparing
with traditionally used ethylene glycol dimethacrylate (EGDMA) reactive diluent, these
new type non-isocyanate urethane dimethacrylates (NUDMA) reactive diluents shows
significant improvements in impact resistance and elongation at break properties. This
improvement in toughness is presumably the result of hydrogen bonds formation in the
168

urethane groups. It was found that the optimum level of the NUDMA reactive diluents
concentration is between 10-20 wt %.
169

CHAPTER VIII

CONCLUSIONS

In this dissertation, four types of organic coatings based on polyester polyols were
prepared: UV-curable unsaturated polyester/poly(meth)acrylate block copolymers,
thermal curable long pot life polyester based polyurethane-urea coatings, thermal curable
non-isocyanate polyurethane coatings, and UV-curable non-isocyanate polyurethane
coatings.
A series of novel saturated polyester (SPE)- and unsaturated (UPE)-based block
copolymers of (meth)acrylates were accomplished by the combination of condensation
polymerization and ATRP. The polymerizations were well controlled and the main chain
double bonds in the unsaturated polyester backbones remained almost unaffected during
polymerization. Because of network formation upon irradiation the UPE-based block
copolymer could be suitable candidate for solvent resistant coating material with superior
properties.
Thermal curable polyester based polyurethane-urea (PUU) coating was
successfully prepared. During the formulation, four different polyester polyols were
chosen as the binders, isophorone diamine (IPDA) was chosen as the chain extender and
also as the reactant for the formation of urea units, and the partially blocked
170

HDI isocyanurate (PBH) was chosen as crosslinker to increase pot life and reduce the
loss the IPDA. As a comparison, the polyurethane coatings (PU) without adding IPDA
were also prepared. With the incorporation of the IPDA, the tensile modulus and tensile
strength of PUU coating showed higher values than those of the corresponding PU
coatings due to the formation of the urea unit and extra physical interaction forces from
the hydrogen bonding among urea groups. With the incorporation of the IPDA, PUU
coating exhibtied higher crosslink density and Tg than the corresponding PU coating.
The hydroxyl terminated, epoxidized, and cyclic carbonate terminated polyesters
were synthesized and characterized by FTIR and NMR. The cyclic carbonate terminated
polyester formation with time was monitored by using IR spectroscopy. Non-isocyanate
polyurethane coatings were prepared by the thermo-curing of the cyclic carbonate
terminated polyester and polyamine.
Three urethane dimethacrylate monomers were synthesized via a non-isocyanate
route. The addition of the non-isocyanate urethane dimethacrylate could reduce the
viscosity of the acrylated polyester (APE) oligomer. The urethane dimethacrylates could
use as reactive diluents for UV-curable coating. Photopolymerization kinetics of non-
isocyanate urethane dimethacrylates was studied. PI Darocur 4265 shows highest overall
conversion and maximum polymerization rate, it was chosen as the PI for
photopolymerization kinetics of reactive diluents and its formulation with APE oligomer.
The polymerization conversion and maximum polymerization rate increase with
increasing initiator concentration in the range from 0.5 % to 4.0 %. The reactive diluents
non-isocyanate urethane dimethacrylate showed lower polymerization overall conversion
and maximum polymerization rate than APE oligomer. But formulation system showed
171

higher polymerization overall conversion and maximum polymerization rate than APE
oligomer.
The new type and more environmental friendly UV curable polyurethane coatings
were formulated using the acrylated polyester (APE) as oligomer and non-isocyanate
urethane dimethacrylates (NUDMA) as reactive diluents. The UV-cured coatings
properties were dependent on the reactive diluents type and content. Crosslink density,
storage and tensile modulus, pencil hardness, chemical resistance, gel content, total water
absorption, and Tg were proportional to the content of the reactive diluents. Comparing
with traditionally used ethylene glycol dimethacrylate (EGDMA) reactive diluent, these
new types of non-isocyanate urethane dimethacrylates (NUDMA) reactive diluents
showed significant improvements in impact resistance and elongation at break properties.
This improvement in toughness is presumably the result of hydrogen bonds formation in
the urethane groups. It was found that the optimum level of the NUDMA reactive
diluents concentration is between 10-20 wt %.

172

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