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
Polybenzoxazines

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

SUMMARY
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

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

Polybenzoxazines are an alternative to traditional
phenolic resins and other thermosetting resins such
as epoxies, unsaturated polyesters and even to high
performance polymers like bismaleimides and
*To whom correspondence should be addressed.
While benzoxazine chemistry is not new, no paper
had been published on the physical and mechanical
properties of polybenzoxazines until Ning and Ishida
studied bifunctional benzoxazine precursors4. The
bifunctional benzoxazine leads to high molecular
weight polymers. Polybenzoxazines provide a
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
precursors exhibit low viscosity, which is
advantageous from a processing point of view.
The majority of monomers undergo volumetric
shrinkage upon polymerization. However, zero
shrinkage or volumetric expansion can be desirable
in many applications, such as coatings, composites,
and precision casting. Shrinkage causes residual
stress and may lead to premature debonding and
microcracks. Bailey et al.6-9 reported spiro ortho
esters and spiro ortho carbonates that polymerize via
a ring-opening reaction, showing volumetric
expansion. They hypothesized that the strained ring
of the monomer opened and occupied a larger volume
afterwards. These spiro ortho compounds were often
mixed with epoxy resins in order to counter the
shrinkage of the epoxy. An example is work of
He et al. where norbornene-spiro-orthocarbonate
(NSOC) was copolymerized with an epoxy resin10,11.
They found that the room temperature density of the
polymer was lower than that of the monomer, while
the Tg and the mechanical properties decreased as
the amount of NSOC increased. In addition to the
aforementioned mechanism of volumetric expansion,
it is thought that the reduction of shrinkage in the
glassy state (<Tg) during the cooling process by
lowering the Tg of the copolymer significantly
contributed to the observed results. The shrinkage in
the glassy region leads to internal stresses since the
molecular motion of the network segments was mostly
restricted in this region. In general, better mechanical
properties are reported with materials showing lower
shrinkage11-13.
The room temperature density (ρRT) of an epoxy resin
with various curing conditions was studied by Pang
and Gillham14. The ρRT of a polymer depends on
many factors, such as curing time, curing temperature,
and cooling rate after the curing reaction. They found
that, at low Tc, the ρRT of both fast and slow-cooled
specimens increased gradually with curing time due
to the densification of the material in the liquid and
rubbery states. The density levels off when the material
reaches the glassy state at a specified Tc. A different
event occurs at moderate Tc. However, the increased
ρRT as a function of curing time is found for fast-
cooled samples. This is contrary to the slow-cooled
samples where the ρRT decreased as a function of
curing time. Both the fast and slow-cooled samples
showed decreased ρRT at a higher Tc. These
phenomena can be explained by the effect of glass
transition temperature and crosslink density on the
thermal shrinkage during the cooling step of the
polymerization reaction.
368
Ishida and Allen reported while using dilatometric
measurements that the maximum shrinkage for
isothermally cured BA-a or the volumetric expansion
coefficient in the glassy state were lower than for
epoxy15. The near-zero shrinkage at room temperature
of fully cured BA-a was observed when the volumes
at room temperature of the amorphous monomer and
the polymer cured at 140°C were compared. At the
isothermal curing temperature of 140°C, the material
underwent approximately 3% shrinkage upon
polymerization until it reached the vitrification point.
The greatest cure shrinkage was found at this
temperature. Above 140°C, the cure shrinkage was
lower. And above 195°C, the material cures either
with no shrinkage or possibly even some expansion.
The BA-a materials are polymerized with low
shrinkage under isothermal conditions. Ishida and
Low reported the effect of intramolecular hydrogen
bonding on the volumetric expansion of benzoxazines
by systematically varying the type of primary amine
used in synthesis16. There is intramolecular hydrogen
bonding between the phenolic OH and the nitrogen
of the Mannich base17,18. The strength of this hydrogen
bonding depends on the electronegativity of the
amine group that is attached to the nitrogen. The
stronger the hydrogen bonding, the greater the
volumetric expansion. In addition, the steric effect of
the amine group also influences the volumetric
changes during cure.
Both near-zero volumetric changes (or expansion)
upon polymerization and fast development of Tg at
low conversions are observed for polybenzoxazines
and are rare among many known polymers. Near-
zero volumetric changes are commonly observed for
many benzoxazine resins15,16. However, the effect of
conversion on the Tg of polybenzoxazines has not
been studied to date. Thus, in addition to the
bisphenol-A based benzoxazine, a fluorinated
benzoxazine is also studied for comparison.
Incorporation of fluorine into polymers can cause a
significant change in the polymer properties. Thus,
if similar behaviour is observed in the fluorinated
benzoxazine, the likelihood of observing the high Tg
increase at low conversions for other benzoxazines
may be high.
The fluorine-containing polymers are also attractive
in the optical and electronic packaging material
industries. The low moisture absorption due to the
hydrophobicity of fluorine-containing polymers has
been reported19. The effect of fluorination on thermal
stability enhancement has also been investigated20.
Owing to the aforementioned results, the synthesis
and characterization of fluorinated polymers have
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
polymeric materials, such as polyimides, polyamides,
polyethers, and polybenzoxazoles21. In the past, an
effort to synthesize the benzoxazine monomers from
fluorinated primary amines has been made22. It was
found that, under neutral conditions, the fluorinated
primary amines were exceptionally unreactive. This
can be explained by the fact that a high basicity of
primary amines is required for ring formation of the
benzoxazine monomer. In this case, the high
electronegativity of fluorine acts to reduce the basicity
of the primary amines, resulting in a very low yield
of benzoxazine monomers. In this work, the bisphenol-
containing hexafluoropropylidene group was used.
After the synthesis and characterization, the
fluorinated benzoxazine monomer was polymerized
via a ring-opening polymerization. Since no
fluorinated polybenzoxazines have been reported in
the literature, the effect of fluorination on the thermal
properties was also evaluated. The thermal properties
of fluorinated benzoxazine polymers were
characterized by differential scanning calorimetry
(DSC) and thermogravimetric analysis (TGA).
The aim of this work was to study effect of curing
conditions on volumetric expansion. The glass
transition temperature of polybenzoxazines is studied
by varying the curing temperature and curing time.
EXPERIMENTAL
Bisphenol-A, aniline (99.5%), 1,4-dioxane,
diethylether, chloroform, sodium sulphate and
formaldehyde aqueous solution (37%) were
purchased from Aldrich. 2,2-Bis(4-hydroxyphenyl)
hexafluoropropane (bisphenol-AF, 97%) was
purchased from PCR, Inc. Paraformaldehyde was
purchased from Fluka. All chemicals were used
without further purification. The benzoxazine based
on bisphenol-A and aniline was synthesized by the
method reported elsewhere4 according to the
following scheme. The monomer, bis-(3,4-dihydro-
6-phenyl-2H-1,3-benzoxazinyl)isopropane is
abbreviated as BA-a. The benzoxazine based on
bisphenol-AF and aniline was also prepared by the
Scheme 1
where R = CH3 or CF3
Polymers & Polymer Composites, Vol. 9, No. 6, 2001
solventless method23. The monomer, bis-(3,4-
dihydro-6-phenyl-2H-1,3-benzoxazinyl)hexafluoro-
isopropane is abbreviated as BAF-a and was
synthesized according to the method reported by Liu
and Ishida 24. Formaldehyde is the common
component for both benzoxazines. The crude
benzoxazines were purified according to a reported
method4. The monomers were prepared according
to the chemical scheme shown below in Scheme 1.
Approximately 2 grams of purified benzoxazine
monomer was degassed in an aluminium pan in a
vacuum oven at 100°C for 6 hours. They were then
cooled to room temperature. The degassed material
was cured isothermally at 135, 145, 155, 165, 175,
and 185°C for 1 to 10 hours in an oven. The volumetric
expansion of cured samples was studied by density
measurement according to ASTM D792 (Method A).
By comparing the density of the monomers with that
of the polymer, the shrinkage or expansion of the BA-
a material can be determined. Only the bubble-free
samples were used for this measurement. The
temperature of the water bath was kept constant at
24±1°C for all density measurements by water
displacement. Seven samples for each condition
were used for this measurement and the average
value is reported.
A Fourier Transform infrared (FTIR)
spectrophotometer (Bomem Michelson MB110) was
used to obtain infrared spectra. The
spectrophotometer was equipped with a liquid
nitrogen cooled, medium band-pass mercury-
cadmium-telluride (MCT) detector. Co-addition of
100 scans was sufficient to obtain good signal-to-
noise ratio, at a fixed resolution of 4 cm-1. All recorded
spectra were displayed in the absorbance mode. The
benzoxazine sample was mixed with KBr powder
and pressed into a pellet for examination. The 1H
nuclear magnetic resonance (NMR) spectrometer
used was a Varian XL-200 NMR spectrometer with a
proton frequency of 200 MHz. The deuterated
chloroform with 1% tetramethylsilane was used as
the solvent. The sample was further examined by size
exclusion chromatograph (SEC) (Waters 486
369
 Mantana Kanchanasopa, Nantaya Yanumet, Kasinee Hemvichian and Hatsuo Ishida
instrument) equipped with a three Styrogel columns
of molecular weight ranging from 50 to 100,000 at a
flow rate of 1 ml/min, with an ultraviolet absorption
detector fixed at 254 nm. The thermal properties of
the benzoxazine samples were studied by a modulated
differential scanning calorimetry (MDSC) (TA
Instruments model 2920) by purging with nitrogen
gas at a rate of 60 ml/min. Approximately 10-15 mg
of the BA-a or BAF-a samples were placed in a
pressure pan. Experiments were run from 30°C to
350°C at a heating rate of 10°C/min.
Thermogravimetric analysis (TGA) was performed
by a High Res TGA 2950 thermogravimetric analyzer
(TA Instruments) at a heating rate of 20°C/min under
a nitrogen atmosphere with a flow rate of 90 ml/min.
RESULTS AND DISCUSSION
The detailed characterization of the benzoxazine
structure by FTIR and SEC is presented elsewhere4.
Although not shown in this paper, a SEC
chromatogram using a UV detector shows the strongest
peak at 10 min retention time, which is assigned to
the difunctional BA-a benzoxazine monomer. The
shoulder of the strongest peak which occurs at a
shorter retention time represents dimers and higher
oligomers. The purity computed by comparing the
area under the highest peak to the shoulder is 98%.
Figure 1 shows representative DSC thermograms of
the uncured and isothermally cured BA-a at the
curing temperature Tc of 155°C for 2 hours. The Tg
appears as an endothermic shift over a temperature
interval in the DSC thermogram. In this study, Tg
was taken as the midpoint of the step-transition. The
residual heat of reaction of the remaining reactants
Figure 1 DSC thermograms of uncured BA-a (top) and
BA-a isothermally cured at 155oC for 2 hours (bottom)
20
15
Heat flow (mW)
10
5
0 -2
-5
-10
-15
0 50 100 150 200
Temperature (°C)
370
(∆Hr) appears as an exothermic peak. The heat of
polymerization is estimated by drawing a straight
line connecting the baseline before and after the peak
and integrating the area under the curve. The area of
the exothermic peak of the uncured sample is the
total heat of reaction (∆Ht). From the value of ∆Ht,
∆Hr, and cure time (t), it is possible to calculate the
fractional conversion or extent of reaction (α) and
rate of reaction (dα/dt) of the curing reaction as:
 ∆Hf 
α =1–   (1)
 ∆Ht 
and
 ∆Hf 
 
dα  ∆Ht  (2)
=
dt ∆t
Figures 2 and 3 show the DSC thermograms of the
materials cured at 155°C for different times and the
materials cured for 3 hours at isothermal Tc of 155,
165, 175, and 185°C, respectively. From these figures,
it is found that both Tg and ∆Hr change monotonically
with Tc and curing time. These phenomena are
illustrated by the plot of Tg vs. curing time in Figure
4. During curing, the glass transition temperature of
the curing system will continuously increase until it
approaches the curing temperature. Then the reaction
mode will change from chemical reaction control to
diffusion control when the viscosity of the reacting
system becomes high, and even stop at the temperature
at which Tg equals Tc, which is defined as vitrification.
Vitrification takes place in materials cured at lower
temperatures than the ultimate glass transition
temperature (Tg∞).
Figure 2 DSC thermograms of BA-a cured at 155oC for
3-6 hours; from top to bottom
4
2
Heat flow (mW)
0
-4
-6
250 300 100 150 200 250 300
Temperature (°C)
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
isothermal curing temperatures of 155, 165, 175, and
185 oC; from top to bottom
4
2 150
Heat flow (mW)
0 120
-2
-4
-6
100 150 200
Temperature (°C)
Figure 4 Glass transition temperature of BA-a cured at
Tc = 155 (●), 165 (◊), 175 (▲), and 185oC (❑)
180
150
120
Tg (°C)
90
60
30
0 2 4 6
Time (h)
The fractional conversions and Tg values of
isothermally cured BA-a at different Tc temperatures
are plotted in Figure 5. The Tg∞ of BA-a was found
to be around 170°C. Unexpectedly, the evolution of
the Tg as a function of the fractional conversion
shows the opposite trend to that of epoxy resin14,25,26.
Gillham and his coworkers reported that the Tg of an
epoxy resin increased very slowly until 0.8-0.9
fractional conversion, after which it increased rapidly.
At very high conversions, the reaction leads to
increased crosslink density and thus influences the
Tg of the epoxy resin significantly, whereas at the
lower conversion, the reaction contributes mostly to
build uncrosslinked molecules. This is contrary to
what was found with the polybenzoxazine where the
Polymers & Polymer Composites, Vol. 9, No. 6, 2001
Figure 5 Relationship between extent of reaction and
glass transition temperature of BA-a cured at Tc = 155
(●), 165 (◊), 175 (▲), and 185oC (❏)
180
Tg (°C)
90
60
30
0.0 0.2 0.4 0.6 0.8 1.0
250 300
Fractional conversion
major increase in Tg takes place during the early
stages of polymerization. When the normalized glass
transition temperature,
cured uncured
Tg − Tg
uncured
Tg∞ − Tg
is calculated for an arbitrarily set fractional conversion
of 0.5, 80% of the glass transition temperature
development has already taken place for the
polybenzoxazine whereas only 28% is found for an
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
associates mechanical and physical properties, is
8 advantageous from the processing point of view.
10
The molecular reason for this unusual phenomenon
is not known at this time but it is hypothesized that
the extensive inter and intramolecular hydrogen
bonding in polybenzoxazine is responsible. As soon
as the degree of polymerization exceeds 3, the
oligomers possess multifunctional phenolic hydroxyl
groups which can form hydrogen bonding networks.
Since no free hydroxyl group is found in the FTIR
spectrum of the partially cured benzoxazine resin,
they must all participate in hydrogen bonding. A
complication arises, however, since intramolecular
hydrogen bonding cannot participate in increasing
the apparent molecular weight. Hence, the relative
ratio of the inter and intramolecular hydrogen bonding
becomes an important criterion for the apparent
molecular weight development through
intermolecular hydrogen bonding. At the present
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
1.2
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
polymer27,28.

1.18 The residual heat of reaction decreased as the cure

30 60 90 120
Tg (°C)
(BA-a). The fluorinated benzoxazine monomer has
been successfully synthesized by the solventless
method 22 using 2,2-bis(4-hydroxyphenyl)
hexafluoropropane.
The thermal behaviour of the BAF-a benzoxazine
polymer was investigated by DSC. All samples were
subjected to isothermal curing for a specified period
of time in an oven. Four different polymerization
temperatures of 155, 165, 175, and 185°C were used.
Polymerization times varied from 10 min to 10 h.
∆HT for the BAF-a benzoxazine monomer was 233.5
J/g. The variation of Tg with polymerization time
under four different isothermal conditions is shown
time increased. The residual heat of reaction can be
transformed in to the fractional conversion by equation
150 180 (1). The increase of fractional conversion with time
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
fractional conversion, the Tgs of samples cured
isothermally at four different temperatures are plotted
in Figure 9 versus the corresponding fractional
conversion. From Figure 9, it is obvious that there
was a relationship between Tg and conversion which
was independent of cure temperature. The
relationship between the glass transition temperature
and the conversion has been studied for some classes
of thermosetting polymers, especially epoxy resin29.
Again, the trend observed for BAF-a-based
polybenzoxazine is the opposite of that for epoxy
resins. However, the increase in Tg as a function of
fractional conversion for BAF-a is not as pronounced
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
220
220
200
200
180
180
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.

20
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
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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
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CONCLUSIONS
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
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