Coordination Polymerization

Ziegler Natta Processes

Stereoregular Polymerization
Cationic Initiation of Vinyl Ethers
Schildknecht et al. Ind. Eng. Chem. 39, 180, (1947)

O
CH2
H3C

CH3

BF3.Et2O

OR

OR

OR

Propane
- 80-60 C

Isotactic vinyl ether

OR

Stereoregular Polymerization
Anionic Polymerization of Methyl Methacrylate,
H. Yuki, K. Hatada, K.Ohta, and Y. Okamoto, J.
Macromol. Sci. A9, 983 (1975)
CH3
O
O

BuLi or
MgBr

H3C OR

Toluene
-78-0 C

OR

OR

OR

Isotactic
H3C OR OR

BuLi
THF -78 C

OR

Syndiotactic

OR

POLYETHYLENE (LDPE)
R
H2C

CH2

20-40,000 psi
150-325 C

H2C

CH2
x

Molecular Weights: 20,000-100,000; MWD = 3-20

density = 0.91-0.93 g/cm3
H3C
Highly branched structure
both long and short chain
branches
Tm ~ 105 C, Xlinity ~ 40%

H3C

CH3

H3C
H3C

C
H2
H3C

15-30 Methyl groups/1000 C atoms

Applications: Packaging Film, wire and cable coating, toys,
flexible bottles, housewares, coatings

CH3
H3C
CH3

Zieglers Discovery
1953 K. Ziegler, E. Holzkamp, H. Breil and H. Martin
Angew. Chemie 67, 426, 541 (1955); 76, 545 (1964).

Al(Et)3 + NiCl2

CH3CH2CH=CH2 + Ni + AlCl(Et)2
100 atm
110 C

+ Ni(AcAc)
+ Cr(AcAc)
+ Zr(AcAc)

Same result
White Ppt. (Not reported by Holzkamp)
White Ppt. (Eureka! reported by Breil)

Al(Et)3 + TiCl4

CH2CH2
1 atm
"linear"
20-70 C Mw = 10,000 - 2,000,000

Polypropylene (atactic)
CH3

CH3

R
*
CH2

n
Low molecular weight oils

Formation of allyl radicals via chain transfer limits achievable

molecular weights for all -olefins

Nattas Discovery
1954 Guilio Natta, P. Pino, P. Corradini, and F. Danusso

J. Am. Chem. Soc. 77, 1708 (1955) Crystallographic Data on PP

J. Polym. Sci. 16, 143 (1955) Polymerization described in French

CH3

TiCl3

CH3

CH3

CH3

CH3

Al(Et)2Cl

Isotactic
CH3

VCl4 - 78 C
Al(iBu)2Cl
O

in

CH3 CH3

CH3

CH3

Syndiotactic

Ziegler and Natta awarded Nobel Prize in 1963

CH3

Polypropylene (isotactic)
CH3

TiCl3

CH3

CH3

CH3

Al(Et)2Cl

Density ~ 0.9-0.91 g/cm3very high strength to weight ratio

Tm = 165-175C: Use temperature up to 120 C
Copolymers with 2-5% ethyleneincreases clarity and
toughness of films
Applications: dishwasher safe plastic ware, carpet yarn,
fibers and ropes, webbing, auto parts

CH3

Polyethylene (HDPE)
CH3

Essentially linear
structure
Few long chain branches, 0.5-3
methyl groups/ 1000 C atoms

Molecular Weights: 50,000-250,000 for molding compounds

250,000-1,500,000 for pipe compounds
>1,500,000 super abrasion resistancemedical implants
MWD = 3-20
density = 0.94-0.96 g/cm3
Tm ~ 133-138 C, Xlinity ~ 80%
Generally opaque
Applications: Bottles, drums, pipe, conduit, sheet, film

Polyethylene (LLDPE)

Copolymer of ethylene with olefin

CH3

CH3

CH3

CH3
CH3

Density controlled by co-monomer concentration; 1-butene (ethyl), or

1-hexene (butyl), or 1-octene (hexyl) (branch structure)

Applications: Shirt bags, high strength films

UNIPOL Process
N. F. Brockman and J. B. Rogan, Ind. Eng. Chem. Prod. Res. Dev.
24, 278 (1985)

Temp ~ 70-105C, Pressure ~ 2-3 MPa

CATALYST PREPARATION
Ball mill MgCl2 (support) with TiCl4 to produce maximum
surface area and incorporate Ti atoms in MgCl2 crystals
Add Al(Et)3 along with Lewis base like ethyl benzoate
Al(Et)3 reduces TiCl4 to form active complex
Ethyl Benzoate modifies active sites to enhance
stereoselectivity
Catalyst activity 50-2000 kg polypropylene/g Ti with
isospecificity of > 90%

Catalyst Formation
AlEt3 + TiCl4

EtTiCl3 + Et2AlCl

Et2AlCl + TiCl4 EtTiCl3 + EtAlCl2

EtTiCl3 + AlEt3 Et2TiCl2 + EtAlCl2
EtTiCl3 TiCl3 + Et. (source of radical products)
Et. + TiCl4 EtCl + TiCl3
TiCl3 + AlEt3 EtTiCl2 + Et2AlCl

General Composition of Catalyst System

Group I
III Metals

Transition Metals

Additives

AlEt3

TiCl4

H2

Et2AlCl

TiCl3

O2, H2O

EtAlCl2

MgCl2 Support

i-Bu3Al

VCl3, VoCL3,
V(AcAc)3

Et2Mg

R C CH

R-OH
Phenols

Et2Zn

Titanocene dichloride R3N, R2O, R3P

Ti(OiBu)4
Aryl esters

Et4Pb

(Mo, Cr, Zr, W, Mn,

HMPA, DMF

Adjuvants used to control Stereochemistry

O
O

CH2CH3
N
H

Ethyl benzoate
2,2,6,6-tetramethylpiperidine
Hindered amine (also
antioxidant)

O
Si
O
O

Phenyl
trimethoxy
silane

Nature of Active Sites

R

Al

R Cl
Cl Ti
Cl Cl
Monometallic site

H3C

CH2

Cl
Ti
Cl
Cl

Al

R
R

Bimetallic site

Active sites at the surface of a TiClx crystal on catalyst

surface.

Monometallic Mechanism for Propagation

Monomer forms -complex with vacant d-orbital

CH2

Cl Ti
Cl Cl

CH3
Cl

CH2

Cl Ti
Cl Cl

Cl

CH3

Alkyl chain end migrates to -complex to

form new -bond to metal

H2 C
CH3
Cl Ti Cl
Cl Cl
CH2

CH2
Cl Ti Cl
Cl Cl

CH3

Monometallic Mechanism for Propagation

Chain must migrate to original site to assure
formation of isotactic structure

H2C
CH3
Cl Ti Cl
Cl Cl
CH2

H3C
CH2
Cl Ti Cl
Cl Cl

If no migration occurs, syndiotactic placements

will form.

Enantiomorphic Site Control Model for

Isospecific Polymerization
Stereocontrol is imposed by initiator active site alone with
no influence from the propagating chain end, i.e. no
penultimate effect
Demonstrated by:

13C analysis of isotactic structures

not
Stereochemistry can be controlled by catalyst enantiomers

Modes of Termination
1. -hydride shift
C H
CH2
Ti

CH2

CH2 H
Al

Ti

Al

CH2
Ti

Al

2. Reaction with H2 (Molecular weight control!)

C H
H H
CH2
Al
Ti
R

CH2

CH3 H
Ti

Al
R

CH2
Ti

Al

Types Of Monomers Accessible for ZN Processes

1. -Olefins

H2C CH2

CH2CH3

CH3

2. Dienes, (Butadiene, Isoprene, CH2=C=CH2)

trans-1,4

cis-1,4

iso- and syndio-1,2

1.2 Disubstituted double bonds do not polymerize

Ethylene-Propylene Diene Rubber (EPDM)

S. Cesca, Macromolecular Reviews, 10, 1-231 (1975)
+

CH3

Catalyst
soluble in
hydrocarbons

VOCl3
Et AlCl
V(AcAc)3 2

.4-.8
.5-.1

0.05

Continuous
catalyst addition
required to
maintain activity

Rigid control of monomer feed ratio required to assure

incorporation of propylene and diene monomers

Development of Single Site Catalysts

R Cl
Cl Ti
Cl Cl
Z-N multisited catalyst, multiple
site reactivities depending upon
specific electronic and steric
environments

Me
Single site catalyst
every site has same
chemical environment

Kaminsky Catalyst System

W. Kaminsky et.al. Angew. Chem. Eng. Ed. 19, 390,
(1980); Angew. Chem. 97, 507 (1985)
Me

X +
X

CH3
*

Al O

*
n

Al:Zr = 1000

Me = Tl, Zr, Hf

Linear HD PE
Activity = 107 g/mol Zr

CH3
Atactic polypropylene, Mw/Mn = 1.5-2.5
Activity = 106 g/mol Zr

Methylalumoxane: the Key Cocatalyst

Al(CH3)3 + H2O

0C

Al
O

Al

Al
O
O
Al
Al
Al

Al O

*
n

n = 10-20

CH3
Al

CH3

toluene

CH3
CH3

MAO
Proposed structure

Nature of active catalyst

Cp2Me

CH3

Al O

*
n

MAO
Cp2Me

CH3

CH3

Al O

CH3
Cp2Me

CH2

Transition metal
alkylation

X
Al
m

X X
Al O Al O
m

Ionization to
form active sites

Noncoordinating Anion, NCA

Homogeneous Z-N Polymerization

Advantages:
High Catalytic Activity
Impressive control of stereochemistry
Well defined catalyst precursors
Design of Polymer microstructures, including chiral
polymers
Disadvantages:
Requires large excess of Aluminoxane (counter-ion)
Higher tendency for chain termination: -H elimination, etc.
Limited control of molecular weight distribution

Evolution of single site catalysts

Date

Metallocene

1950s

Stereo
control

Performance

None

Moderate Mw PE
Some comonomer
incorporation

Me

Early
1980s

None
Me

High MW PE
Better comonomer
incorporation

Synthesis of Syndiotactic Polystyrene

N. Ishihara et.al. Macromolecules 21, 3356 (1988); 19, 2462 (1986)

Ti

Al

CH3

+
n*

Cl

Styrene

Cl

44.1%

Ti Cl
Cl
Cl

Ti

99.2%

syndiotactic polystyrene

Cl
Cl

1.0%

m.p. = 265C

Evolution of single site catalysts

Date
Metallocene
Late
1980s
N

Stereo
control
Slight

Performance
Very High Mw PE,
excellent comonomer
incorporation

Highly
Syndiotactic

Used commercially
for PP

Me

Late
1980s

R
R

Me

Early
1990s

Highly
Used commercially
Isotactic for PP
Me

Technology S-curves for polyolefin

production