Iranian Polymer Journal

14 (11), 2005, 990-999

Gel Time and Exotherm Behaviour Studies of

an Unsaturated Polyester Resin Initiated and
Promoted with Dual Systems
M. Hossein Beheshty*, Hassan Nasiri, and Mehdy Vafayan

Department of Composites, Iran Polymer and Petrochemical Institute, P.O. Box: 14965/115
Tehran, I.R. Iran

Received 6 April 2005; accepted 3 October 2005

ABSTRACT

n this study, the various combinations of low- and high-decomposition temperature ini-

I tiators and dual promoters were used to cure an unsaturated polyester resin. Methyl
ethyl ketone peroxide (MEKP) and acetyl acetone peroxide (AAP) solutions were used
as low-temperature initiators. Benzoyl peroxide (BPO) and t-butyl perbenzoate (TBPB)
were used as medium and high-temperature decomposition initiators, respectively. Gel
time and pseudo-adiabatic exotherm measurements have been used to study the curing
behaviour. It is demonstrated that the low-temperature initiator decomposition does not
interfer with the high-temperature initiator decomposition. It is also found that the
exotherm peak and cure rate have been affected by the decomposition rate of low-tem-
perature initiator at different ways. It is shown in this study that for cobalt naphthenate
and dimethyl aniline (DMA) dual promoters systems, with the increasing of DMA concen-
tration, namely high reactive promoter, causes the exotherm parameters sharply change.
It might be due to the more reactive nature of DMA in comparison with the cobalt naph-
thenate reactivity. Now we can say, a judicious choice of a dual initiator or a dual promot-
er can avoid short time exothermic reactions, so a dual system can be much more effec-
tive than a single one.

Key Words:
dual initiator;
dual promoter;
exotherm behaviour;
gel time;
unsaturated polyester resin.

INTRODUCTION

In the processing of unsaturated a low-temperature initiator and the

polyester resins (for instance in resin other a high-temperature one. The
transfer moulding and compression reason is very simple. Upon charging
moulding processes), it has been a the mould cavity, the resin begins to
common industrial practice to use cure immediately with the help of
(*)To whom correspondence should be addressed. dual initiator systems, consisting of the low-temperature initiator and
E-mail: [email protected] two initiators. One of them would be then completes the curing reaction
Gel Time and Exotherm Behaviour Studies of an... Beheshty M.H. et al.

with the help of the high-temperature initiator. the thermal polymerization of nano-ethylene glycol
The curing reaction is a very important stage in the dimethacrylate (NEGDM) was investigated using mix-
processing of unsaturated polyester resins for produc- tures of two initiators with significantly different half-
ing a composite product. In order to achieve good qual- life temperatures by Xia and Cook [21]. The use of
ity product, the curing reaction should occur in a con- mixtures was found to produce two exotherm peaks
trollable manner. It has now been recognized that [1-3] and to spread the polymerization over a wider tem-
the curing of unsaturated polyester resins is a free rad- perature range in the temperature-ramping DSC exper-
ical chain growth cross-linking copolymerization iment. This reduced the maximum polymerization rate,
between the reactive diluents (e.g., styrene monomer) thus potentially suppressing thermal over-runs and
and the polyester double bonds originating from the temperature gradients during non-isothermal curing. In
unsaturated dicarboxylic acid. The copolymerization is the present paper, we investigated a series of initiators
initiated by peroxides, azo and azine compounds acti- (organic peroxides and perbenzoate), promoters and
vated by metal compounds, tertiary amines and mer- their combinations (dual systems only) for the copoly-
captans or by thermal activation. merization of unsaturated polyester resin mixtures and
A number of studies have qualitatively correlated report on studies of the curing behaviour by gel time
the effect of initiator(s) [4-12] and promoter(s) [13-17], and pseudo-adiabatic exotherm measurements.
on the gel time, cure rate and exotherm behaviour of
unsaturated polyester resins. There have been a few,
more detailed, analyses of the effect of the concentra- EXPERIMENTAL
tion of initiator and promoter on cure behaviour and gel
time of unsaturated polyester resins. Yang and Suspene Materials
[18] measured the gel points during curing and corre- The unsaturated polyester resin used in this study was
lated with initiator concentration, promoter concentra- a 1, 1.15, 1.14 and 1.44 mixture of maleic anhydride,
tion and curing temperature. A correction for taking isophthalic acid, propylene glycol and diethylene gly-
into account heat losses in a quasi-adiabatic reactor has col, respectively containing 40% by weight styrene
been provided by Rojas et al. [19]. They showed that (BUSHEPOL 751129, Bushehr Chemical Industry),
this correction would allow the determination of poly- with an average of 5.88 vinylene groups per unsaturat-
merization kinetics which are not very fast, without ed polyester molecules. The average molecular weight
the use of expensive equipment. Two models based on of the unsaturated polyester resin is 2750 g/mol and the
the free radical polymerization mechanism were devel- equivalent molecular weight/(mol C = C) is 468 g/mol.
oped for predicting the gel time of unsaturated poly- The molar ratio of styrene/unsaturated polyester resin
ester resins cured with t-butyl peroxy-2-ethyl hexa- is 2.7. The unsaturated polyester resin was employed as
noate (PDO) and 2,5-dimethyl-2,5 bis (2-ethyl-hexa- received without removing the inhibitor. We used vari-
noyl-peroxy) hexane (DMB)[20]. Exotherm control in ous amounts of methyl ethyl ketone peroxide (MEKP)

Table 1. Dual initiator systems used in the experiments.

Materials Compositions (wt %) (initiator ratio)

BPO/MEKP 0.00/2.00 0.25/1.75 0.50/1.50 0.75/1.25 1.00/1.00 1.25/0.75
(0) (1/7) (1/3) (3/5) (1) (5/3)
BPO/AAP 0.00/2.00 0.25/1.75 0.50/1.50 0.75/1.25 1.00/1.00 1.25/0.75
(0) (1/7) (1/3) (3/5) (1) (5/3)
TBPB/MEKP 0.00/2.00 0.25/1.75 0.50/1.50 0.75/1.25 1.00/1.00 1.25/0.75
(0) (1/7) (1/3) (3/5) (1) (5/3)
TBPB/AAP 0.00/2.00 0.25/1.75 0.50/1.50 0.75/1.25 1.00/1.00 1.25/0.75
(0) (1/7) (1/3) (3/5) (1) (5/3)

991 Iranian Polymer Journal / Volume 14 Number 11 (2005)

 Beheshty M.H. et al. Gel Time and Exotherm Behaviour Studies of an...

Table 2. Dual promoter systems used in the experiments. Hubner). The measurements of the heat evolved during
curing reaction were conducted using a PL, DSC-1500
Materials Compositions (wt %) (promoter ratio)
differential scanning calorimeter with nitrogen as
+2
DMA/Co 0.0/0.1 0.1/0.1 0.2/0.1 0.3/0.1 0.4/0.1
flushing gas. All the experiments were performed under
(0) (1) (2) (3) (4) isothermal conditions to obtain the heat flow curves.
DMA/Co+2 0.0/0.5 0.1/0.4 0.2/0.3 0.3/0.2 0.4/0.1
(0) (1/4) (2/3) (3/2) (4)
RESULTS AND DISCUSSION

solution containing 9.9% active oxygen and acetyl ace- Dual Initiator Systems
tone peroxide (AAP) solution containing 4.1% active Effect of BPO/MEKP and BPO/AAP Dual Initiators
oxygen as low-temperature initiators supplied by Elf- Figures 1 and 2 illustrate the important role of
atochem with commercial names of Luperox K1 and BPO/MEKP and BPO/AAP as mixture of high- and
Luperox K3, respectively. The chosen medium-temper- low-temperature initiators on the curing behaviour of
ature initiator was dibenzoyl peroxide (BPO) from the unsaturated polyester resin with different composi-
Pamukale Co. and the high-temperature type was t- tions of dual initiators, respectively. Using these figures
butyl perbenzoate (TBPB) with commercial name of we determined, the time-to-peak, exotherm peak and
Trigonox C from Akzo Nobel. Cobalt (II) naphthenate
and dimethyl aniline (DMA) solutions (commercial
grades) were used as promoters. Tables 1 and 2 give a
summary of the various combinations of initiators and
promoters used in the present investigation, respective-
ly. In all formulations illustrated in Table 1, the samples
contained two parts of initiator to one hundred part of
the reaction mixture containing the dual initiators, pro-
moter and unsaturated polyester resin, by weight. Table
2 also shows the samples which contained various parts
of DMA solution to one hundred parts of the reaction
mixture with the Co2+ concentration that is constant
(0.1/100 parts of reaction mixture) and those that con- Figure 1. Measured exotherm of the unsaturated polyester
tained 0.5 parts of promoter to one hundred parts of resin containing 2.0 wt% dual initiator (BPO/MEKP) and 0.5
reaction mixture, by weight. wt% cobalt naphthenate at 20oC. BPO/MEKP ratios are 0,
1/7, 1/3, 3/5, 1 and 5/3 (left to right).

Instrumentation and Procedures

The cure exotherm was measured according to ASTM
D 2471-99. The polyester resin containing cobalt (II)
promoter or its mixture with DMA were mixed with the
appropriate amount of initiators at ambient temperature
and the mixture rapidly mixed for 1 min. Approximately
70 g of this mixture was poured into a paper cup (4 cm
diameter and 7 cm deep) at ambient temperature. The
height of mixture in the paper cup was 5 cm. The time-
temperature data was measured by placing a thermo-
couple in the centre of isolated paper cup connected to
a digital thermometer. Figure 2. Measured exotherm of the unsaturated polyester
The gel time was determined by measuring the resin containing 2.0 wt% dual initiator (BPO/AAP) and 0.5
resistance to the motion of a 3 mm diameter aluminium wt% cobalt naphthenate at 20oC. BPO/AAP ratios are 0, 1/7,
tube probe using a gel time meter (J. Condenhove & 1/3, 3/5, 1 and 5/3 (left to right).

Iranian Polymer Journal / Volume 14 Number 11 (2005) 992

Gel Time and Exotherm Behaviour Studies of an... Beheshty M.H. et al.

Figure 3. Dependence of gel time and time to peak on initia- Figure 4. Exotherm peak versus initiator ratio of dual initia-
tor ratio for an unsaturated polyester resin initiated with 2.0 tors added to the unsaturated polyester resin initiated with
wt% dual initiators and 0.5 wt% cobalt naphthenate at 20oC. 2.0 wt% dual initiators and 0.5 wt% cobalt naphthenate solu-
tion at 20oC.

cure rate (dT/dt) of BPO/MEKP and BPO/AAP dual

initiators. figure shows that the AAP decomposition rate is much
We can notice the gel time and time-to-peak for faster than the one for MEKP. By comparing the
BPO/MEKP and BPO/AAP mixtures in the Figure 3. It isothermal DSC thermograms of AAP and those of
is clearly observed that the gel time and time-to-peak MEKP, it is found that QAAP (heat of reaction for AAP)
show the similar behaviour with respect to the initiators is higher than QMEKP. So we expect a higher exother-
concentration ratio. This behaviour demonstrates that mic peak for BPO/AAP mixture than the one for
the decomposition of the low-temperature initiators BPO/MEKP mixture at any initiator ratio (Figure 4).
(i.e., MEKP and AAP) will be completed when the reac- Figure 6 gives the plots of the cure rate vs. the ini-
tion reaches the gel time. In other words the low-tem- tiator ratio for BPO/MEKP and BPO/AAP systems. It
perature initiator decomposition does not interfere with
the high-temperature initiator decomposition. It is inter-
esting to notice that the gel time and time-to-peak does
not significantly change when the initiator ratios for
each of mixtures are less than 1. A further increase in the
initiators ratio (>1) led to decreasing of the amount of
low-temperature initiators, therefore increasing the
induction time and consequently the gel time. The
above explanation is an evidence for rapidly increasing
of the gel time and time-to-peak, as shown in Figure 3.
The results of the exotherm peak calculated using
Figures 1 and 2 are presented in Figure 4. It is observed
in these plots that BPO/MEKP dual initiator behaviour
is quite different from BPO/AAP mixture behaviour.
The maximum exotherm peak which is observed in
BPO/AAP plot, but not in BPO/MEKP plot, is a result
of a high decomposition rate for the low-temperature Figure 5. DSC Isothermal cure testing at 28oC for an unsat-
initiator. This is demonstrated by the DSC isothermal urated polyester resin containing 2.0 wt% MEKP and AAP
cure testing at 28oC that is illustrated in Figure 5. This promoted with 0.5 wt% cobalt naphthenate.

993 Iranian Polymer Journal / Volume 14 Number 11 (2005)

 Beheshty M.H. et al. Gel Time and Exotherm Behaviour Studies of an...

Figure 8. Measured exotherm of the unsaturated polyester

resin containing 2.0 wt% dual initiator (TBPB/AAP) and 0.5
wt% cobalt naphthenate at 20oC.

respectively. The time-to-peak, exotherm peak and cure

Figure 6. Variations in cure rate versus initiator ratio of dual rate (dT/dt) of TBPB/MEKP and TBPB/AAP dual ini-
initiators added to the unsaturated polyester resin initiated tiators was calculated using these figures (Figures 9-11).
with 2.0 wt% dual initiators and 0.5 wt% cobalt naphthenate By considering the plots in Figure 9 two different
solution at 20oC. behaviour may be observed. For TBPB/MEKP mixture
there is a plateau region (both the gel time and time-to-
is quite clear from this figure that there exists a maxi- peak), which indicates the cure rate will be constant at
mum cure rate with BPO/MEKP system but a final initiator ratio above 0.8. By plotting the cure rate vs.
limit with BPO/AAP system. The reason for this obser- initiator ratio (Figure 11), it is revealed that, there also
vation is a higher decomposition rate for AAP in com- is a plateau region above 0.8. On the other hand, the
parison to MEKP (Figure 5). TBPB/AAP dual initiator plots show that the gel time
and time-to-peak continuously increase with increasing
Effect of TBPB/MEKP and TBPB/AAP Dual Initiators
The effect of TBPB/MEKP and TBPB/AAP as mixture
of high- and low-temperature initiators on the curing
behaviour of the unsaturated polyester resin using dif-
ferent compositions is illustrated in Figures 7 and 8,

Figure 7. Measured exotherm of the unsaturated polyester Figure 9. Dependence of gel time and time to peak on initia-
resin containing 2.0 wt% dual initiator (TBPB/MEKP) and 0.5 tor ratio for unsaturated polyester resin initiated with 2.0 wt%
wt% cobalt naphthenate at 20oC. dual initiators and 0.5 wt% cobalt naphthenate at 20oC.

Iranian Polymer Journal / Volume 14 Number 11 (2005) 994

Gel Time and Exotherm Behaviour Studies of an... Beheshty M.H. et al.

Figure 10. Exotherm peak versus initiator ratio of dual initia- Figure 11. Variations in cure rate versus initiator ratio of dual
tors added to the unsaturated polyester resin initiated with initiators added to the unsaturated polyester resin initiated
2.0 wt% dual initiators and 0.5 wt% cobalt naphthenate solu- with 2.0 wt% dual initiators and 0.5 wt% cobalt naphthenate
tion at 20oC. solution at 20oC.

of TBPB/AAP ratio up to 13 and 18 min, respectively. maximum exotherm temperature with MEKP is 143oC,
It is interesting note that all plots in Figures 3 and 9 while with AAP is 164oC. This maximum exotherm
show a certain initiator ratio which the time-to-peak temperature difference (i.e., 164-143 = 21oC) is a good
and gel time suddenly increase. These points are effec- reason for describing the higher temperature rise due to
tive ratios that the high-temperature initiator (i.e., BPO addition of TBPB to MEKP comparing with AAP.
or TBPB) acts as a main initiator. The longer time is For TBPB/MEKP dual initiators system, it is evi-
needed for decomposition when the high-temperature dent from Figure 11 that cure rate rises to a maximum
initiator content in mixture reaches an effective concen- (75.5oC/min), then falling to a minimum (49.3oC/min)
tration, therefore both the time-to-peak and gel time and finally approaches to a limit (55.1oC/min). When
suddenly increase. the initiator ratio is higher than 0.5, the cure rate for
Figure 10 shows the maximum cure temperatures TBPB/MEKP dual initiators is less than that for the sin-
vs. initiator ratio for the cure reaction of unsaturated gle initiator system (i.e., for MEKP that occuring in a
polyester resin initiated by TBPB/MEKP and initiator ratio equal 0). It can be concluded that TBPB
TBPB/AAP mixed initiators. It is clearly revealed in does not decompose with TBPB/MEKP ratio higher
these plots that a maximum and then a minimum occur than 0.5. It can be seen that raising the initiator ratio to
and finally the plots rise near to or upper than the max- 0.3 (the maximum point of TBPB/MEKP plot in Figure
imum temperatures. Comparing the maximum points in 11) increases the cure rate, therefore TBPB takes part in
plots of Figure 10 with Figure 11, one can easily con- decomposition reaction. Figure 9 (TBPB/MEKP) also
clude that these maximums occur in the same initiator shows that changing the gel time does not occur by
ratios for each one of the mixed initiator systems; i.e. ratio of 0.3, therefore the high-temperature initiator
0.33 and 0.14 for TBPB/AAP and TBPB/MEKP, (TBPB) decomposition takes place. The cure rate plot
respectively. It is found that temperature rise due to of TBPB/AAP dual initiators is almost the same as that
addition of TBPB to MEKP is between 15oC to 20oC, with TBPB/MEKP, but the former sharply drops when
but to AAP is lower than 10oC (Figures 4 and 10). the initiator ratio reaches 1. When the AAP concentra-
Comparing time-temperature curve 0 (denoted in Fig- tion in the initiators mixture is low (i.e., less than
ure 7) with correlated curve in Figure 8, one finds that 1.0%), the heat generation due to decomposition of

995 Iranian Polymer Journal / Volume 14 Number 11 (2005)

 Beheshty M.H. et al. Gel Time and Exotherm Behaviour Studies of an...

Figure 13 shows the gel time and time-to-peak vs.

DMA concentration using data obtained from Figure
12. It is surprising to note that with the higher than
0.2 wt% DMA, the gel time and time-to-peak do no
change, suggesting that they reach a limit value,
because DMA is a very active promoter.
The data in Figure 14 show that increasing the
DMA concentration also increases the exotherm peak
(i.e., the maximum temperature in the plots of Figure
12). It should be noted that with the exception of low
levels (< 0.1wt% DMA), the exotherm peak increases
Figure 12. Measured exotherm of the unsaturated polyester
slowly as the DMA concentration is raised to 0.4 wt%.
resin containing 1.0 wt% MEKP, 0.1 wt% cobalt naphthenate
and various amount of DMA at 20oC.
In general, there is an agreement between the time plots
and exotherm peak ones.
Figure 15 indicates that there is a linear relationship
AAP will not be enough to decompose TBPB, hence between the DMA concentration and the cure rate of
the cure rate suddenly decreases. This is not true for unsaturated polyester resin containing 0.1 wt% Co+2
TBPB/MEKP dual initiator because QMEKP is lower and 1.0 wt% MEKP. The literature [23] shows that the
than QAAP. On the other hand, the plot of TBPB/ rate of free radical polymerization will increase at an
MEKP is laid below the plot of TBPB/AAP (Figure 11) order of 21/2 when it doubles the promoter concentra-
at all the points except the last point. tion, due to the supposition that there is a bimolecular
termination between the radicals. Our results do not
Dual Promoter Systems support this supposition, probably because the poly-
The effect of DMA concentration on the exotherm merization mechanism for the dual promoter systems is
behaviour of the unsaturated polyester resin containing different from those of the single promoter system.
0.1 wt% cobalt naphthenate solution and 1.0 wt% The effect of varying the level of DMA/Co+2 as
MEKP solution is shown in Figure 12. It is clearly mixture of promoters on the curing behaviour of the
observed that the induction time rapidly decreases with unsaturated polyester resin containing 0.5 wt% dual
increasing of DMA concentration. This is due to the promoters and 1.0 wt% MEKP at 20oC is shown in Fig-
reactive nature of DMA that easily attacks MEKP mol- ure 16. At low concentration of DMA, the induction
ecules and rapidly produces alkoxy and peroxy radicals
which initiate the polymerization reactions [22].

Figure 13. Dependence of gel time and time to peak on DMA Figure 14. Exotherm peak versus DMA concentration added
concentration for unsaturated polyester resin initiated with to the unsaturated polyester resin initiated with 1.0 wt%
1.0 wt% MEKP and 0.1 wt% cobalt naphthenate at 20oC. MEKP and 0.1 wt% cobalt naphthenate at 20oC.

Iranian Polymer Journal / Volume 14 Number 11 (2005) 996

Gel Time and Exotherm Behaviour Studies of an... Beheshty M.H. et al.

Figure 17. Dependence of gel time and time-to-peak on pro-

moter ratio for unsaturated polyester resin initiated with 1.0
wt% MEKP and 0.5 wt% dual promoter at 20oC.

Figure 15. Variations in cure rate versus DMA concentration

added to the unsaturated polyester resin initiated with 1.0
wt% MEKP and 0.1 wt% cobalt naphthenate at 20oC.

period is long and the exotherm peak is low. This sug-

gests that the decomposition rate of the DMA is very
faster than it for cobalt naphthenate. When the DMA
level is increased, the induction time is progressively
reduced. In Figures 17, 18 and 19 the gel and peak Figure 18. Exotherm peak versus promoter ratio of
times, exotherm peak and cure rate of samples contain- DMA/Co+2 added to the unsaturated polyester resin initiated
ing 0.5 wt% promoters mixture are plotted as a function with 1.0 wt% MEKP and 0.5 wt% dual promoter at 20oC.
of the promoter ratio (DMA/Co+2) at 20oC.
The exotherm measurements of samples containing
DMA with 0.1wt% Co+2 and 0.5wt% DMA showed a
similar trend for the gel time, time to peak and
exotherm peak (compare Figures 13 and 14 with Fig-
ures 17 and 18), but the trend for their cure rate are
completely different (compare Figure 15 with figure
19). Figures 17, 18 and 19 show that the exotherm

Figure 19. Variations in cure rate versus promoter ratio of

DMA/Co+2 added to the unsaturated polyester resin initiated
with 1.0 wt% MEKP and 0.5 wt% dual promoter at 20oC.

parameters are suddenly decreased or increased up to

0.75 DMA/Co+2 and at higher promoter ratios the
exotherm parameters slowly change or remain approx-
imately constant. A possible reason is that DMA is a
Figure 16. Measured exotherm of the unsaturated polyester
very active promoter, in comparison to the cobalt naph-
resin containing 1.0 wt% MEKP and 0.5 wt% dual promoter thenate, therefore at a definite concentration the free
at 20oC. radical formation due to DMA is completed.

997 Iranian Polymer Journal / Volume 14 Number 11 (2005)

 Beheshty M.H. et al. Gel Time and Exotherm Behaviour Studies of an...

CONCLUSION 4. Rodriguez E.L., The effect of free radical initiators and

fillers on the cure of unsaturated polyester resins, Polym.
The curing behaviour of an unsaturated polyester resin Eng. Sci., 31, 1022-1028 (1991).
initiated with BPO/MEKP, BPO/AAP, TBPB/MEKP 5. Vilas J.L., Laza J.M., Garay M.T., Rodrigues M., Leon
and TBPB/AAP dual initiators and cobalt naphthenate/ L.M., Unsaturated polyester Resins cure: Kinetic, rheo-
DMA dual promoter has been studied by gel time and logic, and mechanical dynamic analysis, II. The glass
pseudo-adiabatic exotherm measurements. It is demon- transition in the mechanical dynamic spectrum of poly-
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choice of dual initiator can avoid short time exothermic worth G.W., Influence of catalyst and reaction exotherm
reactions. Results show that the low-temperature initia- on the cure of unsaturated polyester and vinyl ester lami-
tor decomposition do not interfer with the high-temper- nates, Polym. Compos., 5, 459-481 (1992).
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of BPO/AAP dual initiator system has a maximum using a dual peroxide initiator systems, US Patent No.
point that is a result of high decomposition rate for low- 4,588,798 (1986).
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999 Iranian Polymer Journal / Volume 14 Number 11 (2005)