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Effect of Polymerization Conditions on the Density Changes and Tg of Bisphenol-A...

The Effect of Polymerization Conditions on the Density and Tg of

Bisphenol-A and Hexafluoroisopropylidene-containing

Mantana Kanchanasopa and Nantaya Yanumet

The Petroleum and Petrochemical College,
Chulalongkorn University
Bangkok 10330, Thailand

Kasinee Hemvichian and Hatsuo Ishida*

Department of Macromolecular Science and Engineering
Case Western Reserve University
Cleveland, Ohio 44106-7202, USA

Received: 26th January 2001; Accepted: 22nd May 2001

The volumetric expansion of bisphenol-A and aniline-based benzoxazine (BA-a) has
been studied by comparing the room temperature density of the cured BA-a under
different polymerization conditions with the amorphous BA-a monomer. The glass
transition temperatures (Tg) of BA-a at various degrees of polymerization have been
investigated by differential scanning calorimetry (DSC). The degrees of conversion at
different polymerization temperatures were compared with the respective glass transition
temperatures. It was found that substantial development of Tg occurs at low degrees of
conversion. A fluorinated polybenzoxazine was synthesized from the ring-opening
polymerization of hexafluoroisopropylidene-containing benzoxazine monomer. The
properties of the fluorine-containing polymer were compared to those of nonfluorinated
polybenzoxazine. Fluorine incorporation had a profound effect on the glass transition
temperature of polybenzoxazine. The thermal stability also improved upon fluorination.

INTRODUCTION polyimides. Benzoxazine was first synthesized by

Holly and Cope in 19441 from a phenolic derivative,
Traditional phenolic materials, which are the a primary amine and formaldehyde. However, the
condensation reaction products of phenol and use of benzoxazine as precursor to phenolic resin did
formaldehyde, exhibit good heat-resistant, flame not start until 1973 when Shreiber2 reported the
retardant, and dielectric properties. They are widely formation of oligomeric phenolic compounds made
used in electrical devices, appliances, and from benzoxazines. Riess et al3 studied the synthesis
construction. The use of inexpensive raw materials and reaction of monofunctional benzoxazine
is of particular attraction. While the advantages of compounds. They reported that monofunctional
phenolic resins are considerable, they have also benzoxazines formed only oligomeric materials. They
shortcomings. These include release of water and theorized that the side reaction of the ring opening
ammonia during polymerization, poor molecular reactions compete with the chain propagation and
design flexibility, poor shelf life, and brittleness. lead to low molecular weight products.

Polybenzoxazines are an alternative to traditional While benzoxazine chemistry is not new, no paper
phenolic resins and other thermosetting resins such had been published on the physical and mechanical
as epoxies, unsaturated polyesters and even to high properties of polybenzoxazines until Ning and Ishida
performance polymers like bismaleimides and studied bifunctional benzoxazine precursors4. The
bifunctional benzoxazine leads to high molecular
weight polymers. Polybenzoxazines provide a
*To whom correspondence should be addressed. chemical and structural framework with great

Polymers & Polymer Composites, Vol. 9, No. 6, 2001 367

Mantana Kanchanasopa, Nantaya Yanumet, Kasinee Hemvichian and Hatsuo Ishida

molecular design flexibility5. The benzoxazine Ishida and Allen reported while using dilatometric
precursors exhibit low viscosity, which is measurements that the maximum shrinkage for
advantageous from a processing point of view. isothermally cured BA-a or the volumetric expansion
coefficient in the glassy state were lower than for
The majority of monomers undergo volumetric epoxy15. The near-zero shrinkage at room temperature
shrinkage upon polymerization. However, zero of fully cured BA-a was observed when the volumes
shrinkage or volumetric expansion can be desirable at room temperature of the amorphous monomer and
in many applications, such as coatings, composites, the polymer cured at 140°C were compared. At the
and precision casting. Shrinkage causes residual isothermal curing temperature of 140°C, the material
stress and may lead to premature debonding and underwent approximately 3% shrinkage upon
microcracks. Bailey et al.6-9 reported spiro ortho polymerization until it reached the vitrification point.
esters and spiro ortho carbonates that polymerize via The greatest cure shrinkage was found at this
a ring-opening reaction, showing volumetric temperature. Above 140°C, the cure shrinkage was
expansion. They hypothesized that the strained ring lower. And above 195°C, the material cures either
of the monomer opened and occupied a larger volume with no shrinkage or possibly even some expansion.
afterwards. These spiro ortho compounds were often The BA-a materials are polymerized with low
mixed with epoxy resins in order to counter the shrinkage under isothermal conditions. Ishida and
shrinkage of the epoxy. An example is work of Low reported the effect of intramolecular hydrogen
He et al. where norbornene-spiro-orthocarbonate bonding on the volumetric expansion of benzoxazines
(NSOC) was copolymerized with an epoxy resin10,11. by systematically varying the type of primary amine
They found that the room temperature density of the used in synthesis16. There is intramolecular hydrogen
polymer was lower than that of the monomer, while bonding between the phenolic OH and the nitrogen
the Tg and the mechanical properties decreased as of the Mannich base17,18. The strength of this hydrogen
the amount of NSOC increased. In addition to the bonding depends on the electronegativity of the
aforementioned mechanism of volumetric expansion, amine group that is attached to the nitrogen. The
it is thought that the reduction of shrinkage in the stronger the hydrogen bonding, the greater the
glassy state (<Tg) during the cooling process by volumetric expansion. In addition, the steric effect of
lowering the Tg of the copolymer significantly the amine group also influences the volumetric
contributed to the observed results. The shrinkage in changes during cure.
the glassy region leads to internal stresses since the
molecular motion of the network segments was mostly Both near-zero volumetric changes (or expansion)
restricted in this region. In general, better mechanical upon polymerization and fast development of Tg at
properties are reported with materials showing lower low conversions are observed for polybenzoxazines
shrinkage11-13. and are rare among many known polymers. Near-
zero volumetric changes are commonly observed for
The room temperature density (ρRT) of an epoxy resin many benzoxazine resins15,16. However, the effect of
with various curing conditions was studied by Pang conversion on the Tg of polybenzoxazines has not
and Gillham14. The ρRT of a polymer depends on been studied to date. Thus, in addition to the
many factors, such as curing time, curing temperature, bisphenol-A based benzoxazine, a fluorinated
and cooling rate after the curing reaction. They found benzoxazine is also studied for comparison.
that, at low Tc, the ρRT of both fast and slow-cooled Incorporation of fluorine into polymers can cause a
specimens increased gradually with curing time due significant change in the polymer properties. Thus,
to the densification of the material in the liquid and if similar behaviour is observed in the fluorinated
rubbery states. The density levels off when the material benzoxazine, the likelihood of observing the high Tg
reaches the glassy state at a specified Tc. A different increase at low conversions for other benzoxazines
event occurs at moderate Tc. However, the increased may be high.
ρRT as a function of curing time is found for fast-
cooled samples. This is contrary to the slow-cooled The fluorine-containing polymers are also attractive
samples where the ρRT decreased as a function of in the optical and electronic packaging material
curing time. Both the fast and slow-cooled samples industries. The low moisture absorption due to the
showed decreased ρRT at a higher Tc. These hydrophobicity of fluorine-containing polymers has
phenomena can be explained by the effect of glass been reported19. The effect of fluorination on thermal
transition temperature and crosslink density on the stability enhancement has also been investigated20.
thermal shrinkage during the cooling step of the Owing to the aforementioned results, the synthesis
polymerization reaction. and characterization of fluorinated polymers have

368 Polymers & Polymer Composites, Vol. 9, No. 6, 2001

Effect of Polymerization Conditions on the Density Changes and Tg of Bisphenol-A...

been applied to a number of high performance solventless method23. The monomer, bis-(3,4-
polymeric materials, such as polyimides, polyamides, dihydro-6-phenyl-2H-1,3-benzoxazinyl)hexafluoro-
polyethers, and polybenzoxazoles21. In the past, an isopropane is abbreviated as BAF-a and was
effort to synthesize the benzoxazine monomers from synthesized according to the method reported by Liu
fluorinated primary amines has been made22. It was and Ishida 24. Formaldehyde is the common
found that, under neutral conditions, the fluorinated component for both benzoxazines. The crude
primary amines were exceptionally unreactive. This benzoxazines were purified according to a reported
can be explained by the fact that a high basicity of method4. The monomers were prepared according
primary amines is required for ring formation of the to the chemical scheme shown below in Scheme 1.
benzoxazine monomer. In this case, the high
electronegativity of fluorine acts to reduce the basicity
Approximately 2 grams of purified benzoxazine
of the primary amines, resulting in a very low yield
monomer was degassed in an aluminium pan in a
of benzoxazine monomers. In this work, the bisphenol-
vacuum oven at 100°C for 6 hours. They were then
containing hexafluoropropylidene group was used.
cooled to room temperature. The degassed material
After the synthesis and characterization, the
was cured isothermally at 135, 145, 155, 165, 175,
fluorinated benzoxazine monomer was polymerized
and 185°C for 1 to 10 hours in an oven. The volumetric
via a ring-opening polymerization. Since no
expansion of cured samples was studied by density
fluorinated polybenzoxazines have been reported in
measurement according to ASTM D792 (Method A).
the literature, the effect of fluorination on the thermal
By comparing the density of the monomers with that
properties was also evaluated. The thermal properties
of the polymer, the shrinkage or expansion of the BA-
of fluorinated benzoxazine polymers were
a material can be determined. Only the bubble-free
characterized by differential scanning calorimetry
samples were used for this measurement. The
(DSC) and thermogravimetric analysis (TGA).
temperature of the water bath was kept constant at
24±1°C for all density measurements by water
The aim of this work was to study effect of curing displacement. Seven samples for each condition
conditions on volumetric expansion. The glass were used for this measurement and the average
transition temperature of polybenzoxazines is studied value is reported.
by varying the curing temperature and curing time.
A Fourier Transform infrared (FTIR)
EXPERIMENTAL spectrophotometer (Bomem Michelson MB110) was
used to obtain infrared spectra. The
Bisphenol-A, aniline (99.5%), 1,4-dioxane, spectrophotometer was equipped with a liquid
diethylether, chloroform, sodium sulphate and nitrogen cooled, medium band-pass mercury-
formaldehyde aqueous solution (37%) were cadmium-telluride (MCT) detector. Co-addition of
purchased from Aldrich. 2,2-Bis(4-hydroxyphenyl) 100 scans was sufficient to obtain good signal-to-
hexafluoropropane (bisphenol-AF, 97%) was noise ratio, at a fixed resolution of 4 cm-1. All recorded
purchased from PCR, Inc. Paraformaldehyde was spectra were displayed in the absorbance mode. The
purchased from Fluka. All chemicals were used benzoxazine sample was mixed with KBr powder
without further purification. The benzoxazine based and pressed into a pellet for examination. The 1H
on bisphenol-A and aniline was synthesized by the nuclear magnetic resonance (NMR) spectrometer
method reported elsewhere4 according to the used was a Varian XL-200 NMR spectrometer with a
following scheme. The monomer, bis-(3,4-dihydro- proton frequency of 200 MHz. The deuterated
6-phenyl-2H-1,3-benzoxazinyl)isopropane is chloroform with 1% tetramethylsilane was used as
abbreviated as BA-a. The benzoxazine based on the solvent. The sample was further examined by size
bisphenol-AF and aniline was also prepared by the exclusion chromatograph (SEC) (Waters 486

Scheme 1

where R = CH3 or CF3

Polymers & Polymer Composites, Vol. 9, No. 6, 2001 369

Mantana Kanchanasopa, Nantaya Yanumet, Kasinee Hemvichian and Hatsuo Ishida

instrument) equipped with a three Styrogel columns (∆Hr) appears as an exothermic peak. The heat of
of molecular weight ranging from 50 to 100,000 at a polymerization is estimated by drawing a straight
flow rate of 1 ml/min, with an ultraviolet absorption line connecting the baseline before and after the peak
detector fixed at 254 nm. The thermal properties of and integrating the area under the curve. The area of
the benzoxazine samples were studied by a modulated the exothermic peak of the uncured sample is the
differential scanning calorimetry (MDSC) (TA total heat of reaction (∆Ht). From the value of ∆Ht,
Instruments model 2920) by purging with nitrogen ∆Hr, and cure time (t), it is possible to calculate the
gas at a rate of 60 ml/min. Approximately 10-15 mg fractional conversion or extent of reaction (α) and
of the BA-a or BAF-a samples were placed in a rate of reaction (dα/dt) of the curing reaction as:
pressure pan. Experiments were run from 30°C to
350°C at a heating rate of 10°C/min.
 ∆Hf 
Thermogravimetric analysis (TGA) was performed α =1–   (1)
by a High Res TGA 2950 thermogravimetric analyzer  ∆Ht 
(TA Instruments) at a heating rate of 20°C/min under and
a nitrogen atmosphere with a flow rate of 90 ml/min.
 ∆Hf 
 
dt ∆t
The detailed characterization of the benzoxazine
structure by FTIR and SEC is presented elsewhere4.
Figures 2 and 3 show the DSC thermograms of the
Although not shown in this paper, a SEC
materials cured at 155°C for different times and the
chromatogram using a UV detector shows the strongest
materials cured for 3 hours at isothermal Tc of 155,
peak at 10 min retention time, which is assigned to
165, 175, and 185°C, respectively. From these figures,
the difunctional BA-a benzoxazine monomer. The
it is found that both Tg and ∆Hr change monotonically
shoulder of the strongest peak which occurs at a
with Tc and curing time. These phenomena are
shorter retention time represents dimers and higher
illustrated by the plot of Tg vs. curing time in Figure
oligomers. The purity computed by comparing the
4. During curing, the glass transition temperature of
area under the highest peak to the shoulder is 98%.
the curing system will continuously increase until it
approaches the curing temperature. Then the reaction
Figure 1 shows representative DSC thermograms of mode will change from chemical reaction control to
the uncured and isothermally cured BA-a at the diffusion control when the viscosity of the reacting
curing temperature Tc of 155°C for 2 hours. The Tg system becomes high, and even stop at the temperature
appears as an endothermic shift over a temperature at which Tg equals Tc, which is defined as vitrification.
interval in the DSC thermogram. In this study, Tg Vitrification takes place in materials cured at lower
was taken as the midpoint of the step-transition. The temperatures than the ultimate glass transition
residual heat of reaction of the remaining reactants temperature (Tg∞).

Figure 1 DSC thermograms of uncured BA-a (top) and Figure 2 DSC thermograms of BA-a cured at 155oC for
BA-a isothermally cured at 155oC for 2 hours (bottom) 3-6 hours; from top to bottom
20 4

Heat flow (mW)

Heat flow (mW)


0 -2


-15 -6
0 50 100 150 200 250 300 100 150 200 250 300
Temperature (°C) Temperature (°C)

370 Polymers & Polymer Composites, Vol. 9, No. 6, 2001

Effect of Polymerization Conditions on the Density Changes and Tg of Bisphenol-A...

Figure 3 DSC thermograms of BA-a cured for 3 hours at Figure 5 Relationship between extent of reaction and
isothermal curing temperatures of 155, 165, 175, and glass transition temperature of BA-a cured at Tc = 155
185 oC; from top to bottom (●), 165 (◊), 175 (▲), and 185oC (❏)

2 150
Heat flow (mW)

0 120

Tg (°C)

-4 60

-6 30
0.0 0.2 0.4 0.6 0.8 1.0
100 150 200 250 300
Temperature (°C) Fractional conversion

Figure 4 Glass transition temperature of BA-a cured at

Tc = 155 (●), 165 (◊), 175 (▲), and 185oC (❑) major increase in Tg takes place during the early
stages of polymerization. When the normalized glass
180 transition temperature,
cured uncured
150 Tg − Tg
Tg∞ − Tg
is calculated for an arbitrarily set fractional conversion
Tg (°C)

of 0.5, 80% of the glass transition temperature

90 development has already taken place for the
polybenzoxazine whereas only 28% is found for an
60 epoxy resin25. This implies that a very high conversion
is not necessary for the polybenzoxazine to reach a Tg
close to Tg∞. This early development of Tg, and
30 associates mechanical and physical properties, is
0 2 4 6 8 advantageous from the processing point of view.
Time (h)
The molecular reason for this unusual phenomenon
is not known at this time but it is hypothesized that
The fractional conversions and Tg values of the extensive inter and intramolecular hydrogen
isothermally cured BA-a at different Tc temperatures bonding in polybenzoxazine is responsible. As soon
are plotted in Figure 5. The Tg∞ of BA-a was found as the degree of polymerization exceeds 3, the
to be around 170°C. Unexpectedly, the evolution of oligomers possess multifunctional phenolic hydroxyl
the Tg as a function of the fractional conversion groups which can form hydrogen bonding networks.
shows the opposite trend to that of epoxy resin14,25,26. Since no free hydroxyl group is found in the FTIR
Gillham and his coworkers reported that the Tg of an spectrum of the partially cured benzoxazine resin,
epoxy resin increased very slowly until 0.8-0.9 they must all participate in hydrogen bonding. A
fractional conversion, after which it increased rapidly. complication arises, however, since intramolecular
At very high conversions, the reaction leads to hydrogen bonding cannot participate in increasing
increased crosslink density and thus influences the the apparent molecular weight. Hence, the relative
Tg of the epoxy resin significantly, whereas at the ratio of the inter and intramolecular hydrogen bonding
lower conversion, the reaction contributes mostly to becomes an important criterion for the apparent
build uncrosslinked molecules. This is contrary to molecular weight development through
what was found with the polybenzoxazine where the intermolecular hydrogen bonding. At the present

Polymers & Polymer Composites, Vol. 9, No. 6, 2001 371

Mantana Kanchanasopa, Nantaya Yanumet, Kasinee Hemvichian and Hatsuo Ishida

time, no quantitative data on this ratio is available. Figure 6 Density of BA-a cured at Tc = 155 (●), 165 (◊),
However, qualitatively, a strong intermolecular 175 (▲), and 185 oC (■)
hydrogen bonded IR band is observed, and thus it is
safe to assume that a large number of hydroxyl groups
are participating as intermolecularly hydrogen 1.20
bonded groups18. It is obvious that the apparent
molecular weight of the intermolecularly hydrogen

Density (g/cm3)
bonded molecules develops much faster than the
molecular weight based on covalent bonds alone. It 1.19
is also important to recognize the stiffening role of the
strong chelated intramolecular hydrogen bonds,
O—H—N. It is for these reasons that the Tg of
polybenzoxazine develops quickly at very low 1.18
fractional conversions. Interestingly, a model epoxy
resin that yields one hydroxyl group in every chemical
repeat unit upon polymerization exhibits the
0 2 4 6 8 10
intermediate situation. Again, at the fractional
Curing time (h)
conversion of 0.5, 40% of the glass transition
temperature development was observed, further
implying that hydrogen bonding may indeed be a
major parameter for this phenomenon. the increased percent conversion. Gillham and his
coworkers studied extensively the effect of crosslink
The average room temperature density (ρRT) of the density on the volume of epoxy resin. They reported
monomer and cured BA-a are shown in Table 1. By that increased crosslink density lead to volumetric
comparing the ρRT of this amorphous monomer and expansion14. The free volume measurement by
polymer, the volumetric expansion upon positron annihilation also supports this statement18.
polymerization of BA-a was found to be around It is interesting to note that the ρRT of the cured
1-2% depending on the polymerization conditions. BA-a at 185°C shows the opposite trend to the other
Tc temperatures. At this temperature, the ρRT tends
to increase during the prolonged curing time.
The plot of density vs. curing time is shown in Figure
6. Similar trends are observed for samples cured at
155, 165 and 175°C. The ρRT decreases as a function A plot of density vs. Tg is shown in Figure 7. Most of
of curing time and it is nearly constant at the lower the data fit the curve except for the material
density for long curing times, due to the effect of the polymerized at 185°C. It is possible that the
diffusion controlled reaction and lower rate of polymerization reaction at Tc < Tg∞ is slightly
polymerization. Comparing the ρRT of BA-a cured different from that at Tc > Tg∞. The polymerization
for the same time at various Tc temperatures, it was preferentially takes place at the ortho position of the
found that the higher the Tc, the lower the ρRT due to phenolic structure. The para position is unavailable
since it is occupied by the bond with the quaternary
carbon of bisphenol-A. Although quite unreactive,
Table 1 The average room temperature density the meta position is nonetheless available and can
(ρRT) of the monomer and cured BA-a, for different react when the conditions are favourable. Increased
curing conditions
temperature might provide a sufficient condition for
Cure time (h) 155° C 165° C 175° C 185° C the meta position to react as well. If this reaction
0 1.2000 1.2000 1.2000 1.2000 takes place, the local structure of the benzoxazine
1 1.2002 1.1981 1.1940 1.1857 networks would be quite different from that of the
2 1.1981 1.1873 1.1875 1.1837 ortho-dominated structure. Further study is needed
3 1.1901 1.1871 1.1828 1.1823 to verify this hypothesis.
4 1.1886 1.1814 1.1806 1.1827
5 1.1850 1.1824 1.1814 1.1826
6 1.1840 1.1826 1.1771 1.1810 This fast development of Tg at low conversions is
7 1.1856 1.1823 1.1781 1.1806 unusual. In order to examine whether or not this is
8 1.1845 1.1816 1.1789 1.1814 a common phenomenon among benzoxazine resins,
9 1.1855 1.1806 1.1771 1.1822 bisphenol-AF-based benzoxazine (BAF-a) was used
10 1.1842 1.1834 1.1776 1.1838 to compare with bisphenol-A-based benzoxazine

372 Polymers & Polymer Composites, Vol. 9, No. 6, 2001

Effect of Polymerization Conditions on the Density Changes and Tg of Bisphenol-A...

Figure 7 Relationship between density of BA-a cured at in Figure 8. From the comparison between these two
Tc = 155 (●), 165 (◊), 175 (▲), and 185 oC (❏) and glass polybenzoxazines, we found that, under the same
transition temperature curing conditions, the Tg of the BAF-a
polybenzoxazine was about 40-50°C higher than that
of the BA-a polybenzoxazine. Another interesting
observation found as a result of the fluorination of
polybenzoxazine is that the glass transition
temperature obtained from each polymerization
Density (g/cm3)

temperature was much higher than the cure

1.19 temperature itself (Tg > Tc). This unusual property
has also been reported for some other classes of

1.18 The residual heat of reaction decreased as the cure

time increased. The residual heat of reaction can be
transformed in to the fractional conversion by equation
30 60 90 120 150 180 (1). The increase of fractional conversion with time
Tg (°C) was similar to that of Tg, implying that there is a
correlation between Tg and fractional conversion. In
order to see the relationship between Tg and the
(BA-a). The fluorinated benzoxazine monomer has
fractional conversion, the Tgs of samples cured
been successfully synthesized by the solventless
isothermally at four different temperatures are plotted
method 22 using 2,2-bis(4-hydroxyphenyl)
in Figure 9 versus the corresponding fractional
conversion. From Figure 9, it is obvious that there
was a relationship between Tg and conversion which
The thermal behaviour of the BAF-a benzoxazine was independent of cure temperature. The
polymer was investigated by DSC. All samples were relationship between the glass transition temperature
subjected to isothermal curing for a specified period and the conversion has been studied for some classes
of time in an oven. Four different polymerization of thermosetting polymers, especially epoxy resin29.
temperatures of 155, 165, 175, and 185°C were used. Again, the trend observed for BAF-a-based
Polymerization times varied from 10 min to 10 h. polybenzoxazine is the opposite of that for epoxy
∆HT for the BAF-a benzoxazine monomer was 233.5 resins. However, the increase in Tg as a function of
J/g. The variation of Tg with polymerization time fractional conversion for BAF-a is not as pronounced
under four different isothermal conditions is shown as for BA-a.

Figure 8 Tg of partially cured BAF-a polybenzoxazines

cured isothermally at different temperatures, 155 (●), Figure 9 Tg of partially cured BAF-a polybenzoxazines
165 (◊), 175 (▲), and 185 oC (❏), plotted vs. time cured isothermally at different temperatures plotted
vs. the corresponding fractional conversion
160 160
Tg (°C)

Tg (°C)

140 140
120 120
100 100

80 80

60 60
0 2 4 6 8 10 0 0.2 0.4 0.6 0.8 1
Time (h) Fractional conversion

Polymers & Polymer Composites, Vol. 9, No. 6, 2001 373

Mantana Kanchanasopa, Nantaya Yanumet, Kasinee Hemvichian and Hatsuo Ishida

Figure 10 TGA thermograms of BAF-a and BA-a The benzoxazine monomer was synthesized from a
polybenzoxazines bisphenol containing a hexafluoroisopropylidene
group. The bisphenol-AF-based polybenzoxazine
obtained demonstrated a large increase in the glass
100 transition temperature compared to the bisphenol-
A-based polybenzoxazine. The Tg of bisphenol-A-
Residual weight (%)

based polybenzoxazine was found to be higher than

80 the cure temperature itself, which was not observed
in bisphenol-A-based polybenzoxazine. The
development of the Tg of bisphenol-AF-based
60 polybenzoxazine takes place at a low conversion.
This is the opposite of the trend observed with an
epoxy resin. In addition, the incorporation of a
40 fluorine-containing group was found to improve the
thermal stability of polybenzoxazine.

0 100 200 300 400 500 600 700 800 ACKNOWLEDGMENT
Temperature (°C)
The authors gratefully acknowledge the partial
financial support of the Royal Thai Government. The
A thermogravimetric analysis was performed in order authors are also indebted to the partial financial
to see the effect of fluorination on the thermal stability support of the NSF Center for Molecular and
of polybenzoxazine. The result is shown in Figure 10. Microstructure of Composites (CMMC) which is
From the TGA thermogram of BA-a polybenzoxazine, jointly established by the State of Ohio and EPIC,
weight loss started at around 290oC, and a marked representing industrial members.
decomposition was seen in the range of 350-500°C.
The char yield of this polymer under a nitrogen
atmosphere at 800 ° C was 30%. For BAF-a
polybenzoxazine, the polymer began to lose weight 1. Holly F.W. and Cope A.C., J. Amer. Chem. Soc.,
at 330°C, and a notable decrease of weight was 66, (1944), 1875
observed in the range of 400-600°C. At 800°C, the
char yield of this polymer was determined as 57%. 2. Shreiber H., Ger. Offen. 2225504 (1973); and
From the comparison, it is obvious that the char yield Ger. Offen. 2323936 (1973)
of fluorinated polybenzoxazine was about 28% higher 3. Riess G., Schwob J.M., Guth G., Roche M., and
than that of the nonfluorinated analogue. This increase Lande B., in “Advances in Polymer Science,”
in char yield implies that fluorination had the same B.M. Culbertson and J.E. McGrath, Eds., Plenum,
effect on the improvement of thermal stability of New York (1986) p.27
polybenzoxazine as it does in many other polymers.
4. Ning X. and Ishida H., J. Polym. Sci., Polym.
Chem. Ed., 32, (1994), 1121
5. Ning X. and Ishida H., J. Polym. Sci., Polym.
The density of the BA-a benzoxazine measured at Phys. Ed., 32, (1994), 921
room temperature was investigated as a function of
curing time and isothermal curing temperature. The 6. Bailey W.J. and Katsuki H., ACS Div. Polym.
1-2% volumetric expansion of cured BA-a was found Chem., 14, (1973), 1169
as a function of curing conditions. The higher the
conversion, the higher the volumetric expansion. 7. Bailey W.J., Katsuki H. and Endo T., ACS Div.
Vitrification occurred in the system cured at lower Polym. Chem., 15, (1974), 445
temperatures than 170°C, which is the ultimate glass 8. Bailey W.J., Polym. Preprints, 18, (1977), 17
transition temperature of the cured BA-a. At Tc =
175°C and 185°C (Tc>Tg), vitrification did not occur, 9. Bailey W.J., Mater. Sci. Eng., A126, (1990), 271
so the reaction reached nearly 100% conversion at 10. He P., Zhou Z. and Pan C., J. Mater. Sci., 24,
this cure temperature. At 185°C, minor volumetric (1989), 1528
shrinkage was observed at prolonged curing times,
possibly due to different curing mechanism.

374 Polymers & Polymer Composites, Vol. 9, No. 6, 2001

Effect of Polymerization Conditions on the Density Changes and Tg of Bisphenol-A...

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