Polymers for Advanced Technologies
Volume 5 , pp. 269-274
Synthesis of Unsaturated Polyester
Resins for Large Sized Composites
A. A. Abdel-Azim*, B. H. Mahmoud and M. S. Farhat
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
ABSTRACT
A series of unsaturated polyesters based on phthalic
anhydride (PHA), maleic anhydride ( M A ) , ethylene
glycol (EG), diethylene glycol (DG), triethylene glycol
(TG), propylene glycol (PG), styrene ( S t y ) and acyloni-
trile (AN) were prepared. The molecular weights of the
prepared polyesters were determined by end-group
analysis. The effect of the structure of the resin on its
curing behavior has been investigated. On the basis of
the experimental study, the following were concluded:
( 1 ) The maximum curing temperature (T,,,) is related to
the molecular weight of the glycol incorporated in these
castings. In this context the T,,, was found to decrease
with increasing the molecular weight. Meanwhile the
time to peak temperature t,,, was increasing. (2) The
higher the percentage of A N in the crosslinking monomer
system, the slower a resin cures. (3) The values of T,,,
were found to be influenced to a large extent by the
percentage of A N .
KEYWORDS: Unsaturated polyester, Curing,
Styrene, Ac ry Ionitri le, Synthesis
INTRODUCTION
Fiber-reinforced plastics form a versatile class of
materials that are increasingly replacing conven-
tional structural materials such as metals, wood and
concrete in engineering applications. These mat-
erials, commonly termed FRP, offer a high strength-
to-weight ratio, excellent corrosion resistance ease of
fabrication and versatility of product design in com-
parison with metals. Although both thermosets and
thermoplastics are used as matrix materials for fiber
reinforcement, the thermosets constitute the major
* To whom all correspondence should be addressed.
CCC 1042-7147/94/050269-06
01994 by John Wiley & Sons, Ltd.
segment. Among the thermosetting resins, unsatur-
ated polyesters are the most commonly used matrix
materials for FRP. The world consumption of unsa-
turated polyester resins in composites is of the order
of about 1X lo6 tonnes [l].
Polyesters which have been rendered insoluble
and infusible by crosslinking may be made in several
ways. One of these is to start with an unsaturated
polyester, using its double bonds as sites for copoly-
merization with vinyl monomers. The resulting
polymer is something of a hybrid, therefore, of
condensation and vinyl type polymers. Unsaturated
polyester resins are produced by reacting an unsatur-
ated dibasic acid or a mixture thereof with a satur-
ated dibasic acid with a polyhydric alcohol, and then
adding a polymerizable unsaturated monomer.
These unsaturated polyester resins can be polymer-
ized and cured in the presence of a polymerization
catalyst such as an organic peroxide. The possible
combinations of unsaturated polyester and vinyl
monomer are very great. Copolyesters of various
diols and mixtures of saturated, unsaturated and
aromatic acids permit a wide range of properties to
be obtained with the use of vinyl monomer. On the
other hand, some work has been done on the produc-
tion of polyester resins based on recycled poly(ethy-
lene terphthalate), PET [2, 31. The purified PET scrap
has been depolymerized using different glycols into
glycolized monomers and oligomers. These oli-
gomers were then reacted with unsaturated dibasic
acids or anhydrides to form unsaturated polyester
resins. The properties of polymer concrete obtained
from resins based on recycled PET have been extensi-
vely studied and have been found to be comparable
to polymer concrete made from virgin materials [4-
61.
When large objects are cast from high polymeric
resins, the high exothermic reaction has frequently
been a considerable problem. The crosslinking reac-
tion of unsaturated polyester is a highly exothermic
process, and heat thus liberated tends to increase the
Received 1 October 1993
Revised 29 November 1993
270 I Abdel-Azim et al.
mold temperature and accelerate the curing reaction.
Consequently, the physical and mechanical proper-
ties of a thermosetting material depend upon the
extent of the polymerization reaction during cure or
upon the degree of cure in the molded material.
Determining such dependence is not only important
for better understanding of structure-property rela-
tionships, but is also fundamental in optimizing the
properties of the final product. Therefore, the control
of the rate of heat generation and the temperature
variations during the processing of these materials is
very important in order to achieve the desired degree
of cure of the product. However, the rate of the
polymerization reaction is dependent upon the tem-
perature and the type and concentration of the
monomer and initiator used. Since the concentra-
tions of initiator and accelerator were established [7]
prior to the curing operation, the curing reaction, in
the present study, may be more likely controlled by
means of controlling the curing environment. This
can be achieved by varying the ratios of two compo-
nent monomer systems, styrene and acrylonitrile,
AN.
This work pertains to the preparation of thermo-
setting materials permitting the casting of large sized
composites and eliminating from such casting the
difficulties encountered due to the excessive heat of
curing by altering the polyhydric alcohol (such as
ethylene, EG, propylene, PG, diethylene, DG, or
triethylene, TG, glycols) combinations during prep-
aration of the unsaturated polyesters. A further para-
meter to be investigated is the variation of the ratios
of two copolymerizable monomers, viz. styrene and
AN, for the sake of optimizing the quality of the final
product, namely, the mechanical properties and the
heat evolved during the crosslinking operation.
EXPERIMENTAL
Materials
Polyhydric alcohols (EG, EG, TG and PG), phthalic
anhydride (PHA), maleic anhydride (MA), styrene
and AN were reagent grade and used without further
purification. All chemicals were obtained from
Aldrich.
Apparatus
A 1.0 1 four-necked flask is equipped with a stirrer,
siphon, nitrogen inlet and thermometer, all reaching
below the surface of the solution and a side arm
joined to a 10 ml Dean and Stark receiver equipped
with a tap and a normal water-cooled Leibig con-
denser used for the initial refluxing period. The
position of this can be changed when it is necessary
to distill off the water of the reaction. At the latter
stage, the thermometer was used to measure the
vapor temperature. An inert gas such as carbon
dioxide, nitrogen or the like was bubbled in slow
stream, in order to prevent darkening or to make it
possible to obtain a pale or colorless product; it also
served the added functions of agitation and of expe-
diting the removal of water formed by the reaction.
Exclusion of oxygen was desirable not only because
it causes discoloration, but also it tends to produce
premature polymerization at the elevated tempera-
tures used.
Preparation of Unsaturated Polyesters (UP)
The UP resins were prepared by reacting the appro-
priate amounts of saturated and unsaturated acid
anhydrides and glycols according to the ratios tabu-
lated in Table 1. Six polyesters were prepared by a
similar method [8].Once the various glycols and acid
anhydrides had been weighed and charged into a
kettle, they were constantly agitated and heated. The
temperature was raised to 150°C over 1hr, then to
190°C over a 4 hr period. The temperature was kept
at 190-200°C for 1 hr. At this stage the reflux con-
denser was changed to the distallation position, and
a vacuum of 100-200 mm Hg applied. The tempera-
ture was then lowered to, and maintained at, 170°C
until the acid number of a sample of the polyester
removed through a siphon was 50 or less. This
required about 1 hr. The acid number was deter-
mined by the conventional method [9]. The vacuum
was removed and the reaction product permitted to
cool under nitrogen to 60°C or just below. About
0.01 g of hydroquinone was added as an inhibitor.
AT 60°C the liquid, slightly yellow, polyester was
diluted by a sufficient quantity of styrene or styrene-
AN monomer mixtures to give a 60% solution of the
polyester. The temperature was lowered to room
temperature at which the solution was relatively
stable when stored under nitrogen in a brown bottle.
The acid values were determined by titrating the
solution of the resins in acetone, with 0.2 N standard
alcoholic solution using phenolphthalein indicator.
Determination of Molecular Weight
The molecular weight of each UP was determined by
end-group analysis [8].The unsaturated polyester
resins were analyzed for acid and hydroxyl values,
for the sake of calculating the molecular weights,
before blending these with the monomer.
Determination of Peak Exotherm
The curing exotherm of the copolymerization reac-
tion between the monomer and unsaturated polyes-
ter were measured by a Digitron digital differential
thermometer, type K, model 3202 with a resolution
O.l"C, kindly provided by Geochem Group Ltd,
Chester, UK. The reaction mixture was kept at 35°C
for about 5 min. When the temperature of the
mixture attained 35"C, the appropriate amount of
accelerator and initiator were added successively and
mixed thoroughly for 1 min. The reaction mixture
was poured into two test-tubes and a glass bottle of
5 ml volume. The resin in the test-tubes was cured to
prepare the specimens required for measuring the
mechanical properties whereas that in the glass
bottle was for measuring the curing exotherm. In
order to reproduce the measurements and afford a
comparative study, the glass bottles used in all
 Synthesis of Unsaturated Polyester Resins / 271

TABLE 1. Composition of Different Formulae of Unsaturated Polyester

Resin

Composition Crosslinker
Acid (mol) Glycol (mol) (wt%)
No. Code PHA M A EG DG TG PG Sty. AN

1 la 0.5 0.5 1.10 - - 40 -

lb 0.5 0.5 1.10 - - 36 4
lc 0.5 0.5 1.10 - - 32 8
Id 0.5 0.5 1.10 - - 28 12
le 0.5 0.5 1.10 - - 24 16
2 20 0.5 0.5 0.55 0.55 - 40 -
2b 0.5 0.5 0.55 0.55 - 36 4
2c 0.5 0.5 0.55 0.55 - 32 8
2d 0.5 0.5 0.55 0.55 - 28 12
2e 0.5 0.5 0.55 0.55 - 24 16
3 30 0.5 0.5 0.55 - 0.55 40 -
3b 0.5 0.5 0.55 - 0.55 36 4
3c 0.5 0.5 0.55 - 0.55 32 8
3d 0.5 0.5 0.55 - 0.55 28 12
3e 0.5 0.5 0.55 - 0.55 24 16
40 0.5 0.5 0.55 - - 0.55 40 -
4 4b 0.5 0.5 0.55 - - 0.55 36 4
4c 0.5 0.5 0.55 - - 0.55 32 8
4d 0.5 0.5 0.55 - - 0.55 28 12
4e 0.5 0.5 0.55 - - 0.55 24 16

5 50 0.5 0.5 - 0.55 - 0.55 40

5b 0.5 0.5 - 0.55 - 0.55 36 4
5c 0.5 0.5 - 0.55 - 0.55 32 8
5d 0.5 0.5 - 0.55 - 0.55 28 12
5e 0.5 0.5 - 0.55 - 0.55 24 16
6 60 0.5 0.5 - 0.55 0.55 - 40 -
6b 0.5 0.5 - 0.55 0.55 - 36 4
6c 0.5 0.5 - 0.55 0.55 - 32 8
6d 0.5 0.5 - 0.55 0.55 - 28 12
6e 0.5 0.5 - 0.55 0.55 - 24 16

measurements were of the same volume. The ther-
mocouple probe of the digital thermometer was
immersed in a narrow tube containing silicon oil
which was inserted into the bulk of the reaction
mixture placed in the glass bottle. The reaction
temperature was reported at different times. It is of
interest to mention that the zero time was considered
as the moment at which the initiator was added to
the reaction mixture. The recorded temperatures
were plotted versus time. The maximum curing
temperature could be detected as the highest value in
the curve, peak exotherm temperature (T,,,), where-
as t,,, is the time required to reach T,,,.
To elucidate the influence of composition of the
reaction mixture on the curing temperature and
curing time, the concentration of methyl ethyl keton
peroxide, MEKP (initiator), and cobalt octoate, CO
(accelerator), were kept constant over the curing
reactions. The formulation used for curing was
resin :initiator :accelerator = 100 :2 :0.2 (parts by
weight) [7].
RESULTS AND DISCUSSION
Molecular Weight
Molecular weight determination through end-group
analysis requires the polymer to contain a known
number of determinable groups per molecule. The
long-chain nature of polymers limits such groups to
the end groups. Thus the method is usually referred
to as end-group analysis [lo]. Since methods of end-
group analysis count the number of molecules in a
given weight of sample, they yield the number-
average molecular weight for polydisperse materials.
The method becomes insensitive at high molecular
weights, as the fraction of end groups becomes too
small to be measured with precision. Although pub-
lished procedures [lo] often indicate that loss of
272 I Abdel-Azim et al.
precision occurs at molecular weights above 25,000,
there is no doubt that the adoption of more sensitive
techniques, such as gas chromatography or mass
spectrometry to estimate the reaction products, can
raise this limit by at least a factor of 10. Similar
considerations apply to the use of infrared spectros-
copy to measure end groups.
End-group analysis in condensation polymers
usually involves chemical methods of analysis for
functional groups. Carboxyl groups in polyesters [111
are usually titrated directly with bases in alcoholic
solvents and hydroxyl groups are usually determined
by reacting them with a titratable reagent [12]. The
chemical method used in determining the molecular
weight of the polyesters prepared in the present
study is described in detail in [8]. The resultant
molecular weights are tabulated in Table 2 in con-
junction with the acid number of the produced
polyesters. The highest molecular weight, M, = 2438,
was obtained for formula no. 1for which the EG was
used as a unique glycol for constructing the unsatur-
ated polyester. We believe that the accuracy of the
determined values is good enough since the highest
molecular weight is less than 25,000 as previously
established [lo]. When l$-pentanediol was used in
conjunction with maleic anhydride, for synthesis of
unsaturated polyester, Larez et al. [13] obtained an
unsaturated polyester with a reaonably high molecu-
lar weight, M,=3307, as compared with that
obtained with lower glycols [14,151.
Horie et al. [16] obtained polyester fumarate
resins by reacting fumaric acid, succinic acid and
diethylene glycol. The range of the resultant molecu-
lar weight’s range was 2700-3300 and was found to
depend to a large extent on the variation of the
fumaric to succinic mole ratio.
Curing Behavior of Unsaturted Polyester Resins
Effect of Crosslinking Vinyl Monomers. For compar-
ison purposes later, it is of interest to present the
curing behavior of the resin with a single initiator
system. Figure 1give plots of the curing exotherms of
formula no. 1. Similar plots for formulae 2-6, not
produced here, were obtained. These formulae, viz.
1-6, were diluted with unsaturated monomer sol-
vents. Variations in the type and amounts of indivi-
dual components allow an enormous flexibility in the
design of resin formulations. The solvents comprised
acrylonitrile (AN) in admixture with styrene over the
TABLE 2. Acid Number and Molecular Weights of
Unsaturated Polyesters (Formulae 1-6)
~
Acid number
Formula (mg K O H / g polymer) Molecular weight
17.9 2438
18.7 21 23
22.3 201 0
27.35 1796
31.9 1543
19.07 2230
120 I I
s
c
80
E
0,
a,
60
4-
40
I I I I I
0 5 10 15 20 25
time (min)
FIGURE 1. Curing exotherms of formula no. 1
dissolved in different styrene-AN mixed solvents having
different percentages of AN as a function of time.
range of O-4O0/o AN. The ratio of unsaturated polyes-
ter: solvent was 60: 40. Consequently, 0, 4, 8, 12 and
16% by weight of AN, based on the total weight of
the resin mixture, were used. The cured resins are
designated here as copolymer na, nb, nc, nd and ne,
respectively, where n is the number given to the
formulae, i.e. 1-6.
As may be seen in Fig. 1, the induction period
increases by increasing the AN content in the mix-
ture. This leads to an increase in the time required
for complete curing (tmax). A similar behavior is
observed in all other exotherms which represent the
heat evolved during curing of formulae 2-6 which
dissolved ion different mixed monomer solvents. It
has been established [17] that the vinyl monomers
generally yield polyester blends that are readily
polymerized at room temperature with the aid of a
suitable initiator-accelerator system, whereas the
ally1 monomers can be polymerized with polyesters
only at higher temperatures. The acrylates and meth-
acrylates lie somewhere between these two types,
and cure only slowly at room temperature. This is the
case in the present work, where the curing time is
prolonged by increasing the content of the acryloni-
trile monomer.
Table 3 shows the measured values of t,,, and the
maximum heat evolved (Tmax)upon curing with the
percentage of AN. It is obvious that there is an
increase in t,,, with increasing content of AN in the
mixed monomer solvent. As an example, Table 3
shows that the maximum curing time increases regu-
larly from 8 min (copolymer la) to 21 min (copolymer
le) as AN content increases from 0.0% to l6%,
respectively. This increase was found to follow eq.
(1):
t,,, = [2.8515 + 0.4346(AN)1’2] (1)
The correlation coefficient of eq. (1)was found to be
0.9908.
The effect of monomers on exotherm tempera-
tures is of some importance, especially in appli-
cations where low peak temperatures of exotherms
are required.
Table 3 also shows that the percentage of AN has
no significant effect on the maximum heat evolved
 Synthesis of Unsaturated Polyester Resins I 273

(T,,) when AN content exceeds 8%, for which higher yield must exhibit a different composition
T,, = 107.5"C for co-polymer lc. With respect to the from that produced originally. The reactivity ratio, Y,
other formulae, the T,,-AN% dependencies show a of styrene (1):AN (2) has been reported [lo] as
maximum at 12% AN for formulae nos. 2 and 3 or a Y, = 0.4 and r2= 0.04. That means that styrene prefers
maximum at 8% AN for formulae nos. 4, 5 and 6. to add the other monomer AN about twice as fast as
Unfortunately, there are no literature values for its own. Meanwhile, the AN reactivity ratio, Y,=
the heat generation during curing with styrene-AN 0.04, is very close to zero, which indicates that AN
mixtures to compare our figures. However, it has readily reacts with styrene monomer. The exotherms
been established [17] that vinyl monomers produce of the reaction which is caused by the replacement of
more heat energy than acrylates and methacrylates. the double bond, in the unsaturated polyester, by
This is so only when the polyester is dissolved in two single bonds via a copolymerization reaction
either one of these monomers. Hayes [18]studied the with styrene depends on the concentration of styrene
copolymerization of styrene and styrene- in the solvent mixture. This may explain the decrease
acrylonitrile with polybutadienes. The author found in the heat evolved during the curing process at
that when styrene is the sole monomer the reactivity higher ratios of AN in the solvent mixture.
of polybutadiene and the temperature effects are less It may be assumed that each styrene molecule
intense than when styrene-acrylonitrile mixtures are reacts with the neighboring polyester chain and AN
used. molecules. The network formed in this fashion
In the present work, when AN is used in con- would be very tight, unless some of the C=C bonds
junction with styrene, the exothermic temperature of the polyester did not react. As was proposed in
increases. This behavior agrees with the finding of earlier study [19],many pendant C = C groups may
Hayes [18]. In this context, we speculate that the be buried in the microgel particles of the polyester
styrene provides the link between the unsaturated and further reaction with styrene and AN requires
polyester and the AN, since styrene copolymerizes their diffusion into the core of the microgels. This
readily with both fumaric unsaturation and AN. may lead to an increase in tmax.With the excess of AN
Copolymers generally possess a composition differ- (less reactive monomer), another possibility is simul-
ent from that of the initial monomer mixture, taneous homopolymerization of the AN monomer to
provided in each case that the polymerization does form larger segments between the polyester chains
not reach 100% conversion. The composition and subsequent polyester-poly(styrene/AN) cross-
depends on the reactivity (measured as rate con- linking. Such a process may lead to a decrease in
stants) and the concentrations of growing ends (e.g. compressive strength.
free radical) and monomers .In copolymerization, the
reactive monomer will polymerize preferentialy. The Eflect of Glycols. The choice of glycols offers a great
copolymer formed at low yields will therefore con- latitude in the design of polymer backbones. A great
tain more of the more reactive monomer. The actual variety of glycols is available and glycols are often
composition depends on the composition of the used in combination. It is important to note that the
monomer mixture and the difference in reactivity of use of glycols in any application is greatly dependent
the monomers. The consumption of the more reac- on the level of fumarate crosslinking density [20].
tive monomer, however, means that the remaining Reactions of thermoset resins are exothermic, in
monomer mixture will become deficient in this general, and therefore the control of temperature
monomer, so that the copolymer that is formed at a during cure is of great importance in controlling the
quality of products. An investigation dealing with
complex systems, such as the curing reactions and
TABLE 3. Properties of Different Formulae
processing of thermoset resins, requires a greater
Cop0 ly rner" attention to all the parameters influencing this ope-
Formula Parameter a b c d e ration. One of these parameters is the type of the
glycols incorporated in the polymers. In this context,
1 T,, ("C) 70.5 85.0 107.5 108.0 108.0 linear polyester fumarates of different degrees of
t,,, (rnin) 8.0 14.5 16.0 19.2 21.0 unsaturation [20]and different glycol combinations
2 T, ("C) 49.0 52.0 61.0 66.0 62.0 were compared. Figure 2 shows the variation of T,,,
f,,, (rnin) 16.0 25.0 29.0 33.0 44.0 and t,, of different formulae, dissolved in styrene
monomer, as a function of the type of glycol incor-
3 T,, ("C) 41.0 43.0 45.0 49.5 48.5 porated in their backbone. It should be pointed out
f,,, (rnin) 15.0 36.0 47.0 55.0 62.0 that the maximum curing temperature is related to
4 T, ("C) 47.0 59.5 93.6 85.0 64.5 three different parameters: (1)type of monomer; (2)
f,,, (rnin) 15.0 17.5 19.2 24.0 32.5 molecular weight of glycol; and (3) the equivalent
5 T, ("C) 43.7 44.0 56.0 54.0 52.0 polymerizable double bonds (EPDBs) of the unstur-
f,,, (rnin) 16.0 30.0 32.0 41.0 47.0 ated polyester resin. Comparing the formulae con-
44.5 43.5 taining EG as one of the components in the main
6 T,, ("C) 38.5 41.0 44.5
f,,, (rnin) 18.0 52.0 65.0 84.0 93.0 chain of the polymer reveals that T,,, decreases with
increasing molecular weight of glycol. When EG is
" Compositions of different formulae and copolymers used along (copolymer no. la), T,, recorded the
are given in Table 1. highest value (70.5"C). This value reduces considera-
bly to 49°C and 41°C on replacing half of the quantity
274 J Abdel-Azim et al.
of EG with DG and TG (copolymers nos. 2a and 3a)
respectively. It is of interest to note that the value of
+
T,,, for the copolymer containing EG PG (copo-
lymer No. 4a) is slightly lower than that for the
copolymer containing EG + DG, although the mole-
cular weight of DG is higher than that of PG. This
may be attributable to the effect of EPDBs since they
are higher in the former case 1201. It is obvious that
the variation in the types of glycol and their combi-
nations leads to different behavior of exothermic
temperature. This may be due to the differences in
the molecular weights of the repeating units of the
unsaturated polyesters; consequently, this variation
of molecular weights lead to the variation of EPDBs.
The T,, of the copolymer containing DG in conjunc-
tion with PG (copolymer no. 5a), as shown in Fig. 2,
reduces from 43.7"C to 38.5"C on replacing PG with
TG (copolymer no. 6a). This finding confirms the
speculation that T,,, decreases with increasing mole-
cular weight of the glycol.
Values of t,,, for different resins under investi-
gation are also shown in Fig. 2. It is seen that, apart
from copolymer no. la, values ranging between 15
and 18 min are obtained. Here it should be pointed
out that a faster curing reaction is obtained when EG
is used as a sole glycol. Meanwhile, the other types
of glycols and their combinations, even with EG,
produce unsaturated polyester resins having longer
curing times combined with less heat evolved.
CONCLUSIONS
The exotherm temperatures and curing time of unsa-
turated polyester resins can be manipulated per
processing requirements by varying the relative
amounts of two monomers incorporated in manufac-
turing the resin. Similarly, they can be controlled by
using two types of glycols having different molecular
weights for constructing the unsaturated polyester
resins. It has been established that the maximum
curing temperature is related to the molecular weight
of the glycol incorporated in the unsaturated polyes-
ter. In this context, the T,, is decreased with increas-
ing molecular weight. Meanwhile, the time to peak
temperature t,,, increases. Inclusion of AN in the
crosslinking monomer system leads to an increase in
both T,,, and,,,t . The increase in T,, is limited to a
definite range of concentration after which this para-
meter tends to saturate or to start to decrease again.
Unsaturated polyester resin, having EG combined
with a higher molecular weight glycol, would be best
suited for processes such as large object molding,
where a low temperature is desirable. These formu-
lae would definitely benefit the large moulding
industries by offering versatility in processing and
properties over conventional resins.
The mechanical and dynamic mechanical proper-
ties of these resins are being investigated and will be
reported in a subsequent publication.
REFERENCES
1. R. V. Utpal and V. M. Nadkami, lnd. Eng. Chem. Res.,
26(2), 194 (1987).
2. K. S. Rebeiz, D. W. Fowler and D. R. Paul, Plastics
Engineering, February, 33 (1991).
3. S. C. Rustagi, D. P. A. Dabholkar, J. K. Niham, M. N.
Marathe and K. B. Iyer, Indian Patent 145 323 (1977).
4. K. S. Rebeiz, D. W. Fowler and D. R. Paul,
Po1ym.-Plast. Technol. Eng., 30(8), 809 (1991).
5. K. S. Rebeiz, D. W. Fowler and D. R. Paul, J. Appl.
Polym. Sci., 44, 1649 (1992).
6. K. S. Rebeiz, D. W. Fowler and D. R. Paul, Proceedings
of the Third International Symposium on Mechanics of
Polymer Composites, the Institute of Theoretical and
Applied Mechanics of the Czechoslovak Academy of
Sciences, Prague, 16-18 .April, p. 367 (1991).
7. E. S. Nasr and A. A. Abdel-Azim, Polym. Adu.
Technol., 3, 407 (1992).
8. W. R. Sorenson and T. W. Campbell, Preparative
Method of Polymer Chemist ry, Interscience, New York,
p. 155 (1968).
9. J. Urbanski, W. Czerwinski, K. Janika, F. Majewska
and H. Zowall, Handbook of Analysis of Synthetic
Polymers and Plastics, Ellis Honvood, Chichester, UK
(1977).
10. F. W. Billmeyer Jr, Textbook of Polymer Science, 2nd
edn, Wiley-Interscience, New York (1971).
11. H. A. Pohl, Anal. Chem., 26, 1614 (1954).
12. A. Conix, Makromol. Chem., 26, 226 (1958).
13. V. Larez, J. Crisobal and A. Gilberto, Polym. Bull., 26,
313 (1991).
14. V. Larez, J. Cristobal, P. Mendoza and A. Gilberto,
Polym. Bull., 22, 513 (1989).
15. V. Larez, J. Cristobal, P. Mendoza and A. Gilberto,
Polym. Bull., 23, 577 (1990).
16. K. Horie, I. Mita and H. Kambe, J. Polym. Sci., A-2, 8,
2839 (1970).
17. N. M. Bikales, Encyclopedia of Polymer Science and
Technology, vol. 11, Wiley, New York.
18. R. A. Hayes, J. A p p l . Polym. Sci., 19, 993 (1981).
19. Y. S. Yang and L. Lee, J . Polym., 29, 1793 (1988).
20. A. A. Abdel-Azim, E. S. Nasr and M. S. Farhat, Polym.
J., 26(4), 423 (1994).