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Polymer International Polym Int 50:129134 (2001)

Control of gel time and exotherm behaviour


during cure of unsaturated polyester resins
Wayne D Cook,1* Michelle Lau,2 Mansour Mehrabi,2 Katherine Dean1 and
Marcus Zipper2
1
Department of Materials Engineering, Monash University, Clayton, Victoria 3168, Australia
2
Cooperative Research Centre for Polymers, Business Park Drive, Clayton, Victoria 3168, Australia

Abstract: The curing behaviour of an unsaturated polyester resin has been studied by gel time and
pseudo-adiabatic exotherm measurements. The gel time corresponded closely with the initial rise in
exotherm temperature. Incorporation of tert-butyl catechol inhibitor increased the gel time in a linear
fashion and the exotherm was similarly delayed. An increase in the concentrations of initiator (either
methyl ethyl ketone peroxide or acetyl acetone peroxide) or cobalt octoate accelerator decreased the
gel time in a reciprocal fashion and increased the rate of polymerization. These results are tted to a
theoretical model for inhibition and initiation.
# 2001 Society of Chemical Industry

Keywords: gel time; exotherm; unsaturated polyester; cure kinetics; inhibition

INTRODUCTION predicted the effect of MEKP and cobalt salt on the gel
Many applications for thermosets, such as large time of unsaturated polyester cure, while Ramis and
mouldings and in situ castings, require that the resin Salla12 derived an expression for the cure kinetics of
be cured without external heating. The most common polyester resins with varying levels of inhibitor in an
thermoset group, unsaturated polyester resins, are unaccelerated polyester initiated by benzoyl peroxide.
usually cured at ambient temperature by free radical For the related styrene/divinyl benzene system, Batch
polymerization through the use of peroxides and and Macosko13 also derived an expression for the cure
catalysts which accelerate (or promote) the peroxide kinetics with varying levels of diphenylpicrylhydrazyl
decomposition to free radicals. Methyl ethyl ketone inhibitor and azobisisobutyronitrile initiator.
peroxide (MEKP) is one of the more frequently used Most detailed studies of the effect of the concentra-
organic peroxides for free radical polymerization at tions of initiator, accelerator and inhibitor have been
ambient temperatures, and a cobalt salt is commonly performed under isothermal or temperature-ramping
employed as the accelerator.13 Inhibitors, such as conditions. Although these techniques provide a more
phenols or quinones, react with the initiating or controlled experimental environment, they cannot be
propagating radical, producing a radical of very low related directly to the application conditions for large
reactivity,3,4 thus increasing the storage life of the sections for which the polymerization occurs under
polyester resin and also providing an induction stage almost adiabatic conditions. The importance of under-
during which the resin can be processed before cure. standing the curing behaviour under adiabatic condi-
Because a three-dimensional network develops shortly tions has been emphasized by Salla and Martin14 in
after the start of free radical polymerization,5,6 the their work on predicting adiabatic exotherm curves.
control of the gelation time and cure rate of polyester Therefore, in the present study, the kinetics of free
resins is vital to their use in applications such as resin radical initiation of polyester resins are investigated by
infusion, resin spraying and hand lay-up, and so it is measurement of the gel time and pseudo-adiabatic
important to be able to understand how the induction exotherm behaviour for resins initiated by varying
process depends on the initiator system. amounts of two types of peroxide, a cobalt accelerator
A number of studies have qualitatively correlated and a free radical inhibitor, and the results are inter-
the effect of initiator,13,5,79 accelerator1,2,810 and preted in terms of a gel-time model.
inhibitor1,3 on the gelation, cure rate or exotherm
behaviour of unsaturated polyester resins. There have
been a few, more detailed, analyses of the effect of the EXPERIMENTAL
concentration of initiator and accelerator on the cure The unsaturated polyester resin used was a com-
behaviour of polyester resins. Yang and Suspene11 mercial resin supplied by Huntsman Chemical Co

* Correspondence to: Wayne D Cook, Department of Materials Engineering, Monash University, Clayton, Victoria 3168, Australia
E-mail: wayne.cook@eng.monash.edu.au
(Received 11 January 2000; revised version received 23 June 2000; accepted 27 July 2000)

# 2001 Society of Chemical Industry. Polym Int 09598103/2001/$30.00 129


WD Cook et al

Australia Pty Ltd as Aropol 4021 and was a poly(pro- (Texp) was corrected for heat loss to the environment
pylene glycolorthophthalatediethylene glycolfuma- using the heat balance method of Rojas et al. 15
rate) resin containing approximately 35 wt% styrene Z
(Fig 1). This resin was initiated with varying amounts Tcorr Texp U =Cp Texp T0 dt 1
(up to 3 wt%) of methyl ethyl ketone peroxide
(MEKP) supplied by Laporte Australia as MEKP- where Tcorr is the corrected temperature, T0 is the
NA-1, which is a 40% solution in dimethyl phthalate ambient temperature, Cp is the specic heat (which is
and contains a mixture of species such as illustrated7 in assumed to be constant), t is the reaction time and U is
Fig 1, or acetyl acetone peroxide (AAP; see Fig 11) the global heat transfer coefcient per unit mass
supplied by Laporte Australia as AAP-NA-2 in a 35% (which is assumed to be constant). The U/Cp ratio
solution in diacetone alcohol and was accelerated with was calculated from the cooling curve when the poly-
varying amounts (up to 0.8 wt%) of cobalt octoate in a merization had ceased.
6 wt% of a solution of white spirit, supplied by Thor At a specic extent of reaction (x), the heat
Chemicals, Australia. Additional inhibitor (up to generated up to that stage (xDH, where DH is the
0.15 wt%) was added to the resin in the form of 4- total heat of polymerization in J/g) can be approxi-
tert-butyl catechol (TBC) solution (see Fig 1) supplied mately equated with the heat required (CpDTcorr) to
by Huntsman Chemical Co Australia Pty Ltd as a cause a temperature rise in the sample of DTcorr. If the
40 wt% solution in monopropylene glycol mono- heat capacity of the curing resin is assumed to be
methyl ether. constant, then the corrected exotherm curve is an
The polyester was mixed with the appropriate approximate indication of the degree of cure as shown
amount of the peroxide initiator at 25 C; then the by the relation
requisite amount of cobalt accelerator was added and
Cp DTcorr
the mixture rapidly mixed. Approximately 70 ml of this x 2
mixture was poured into a polyethylene cup at 25 C DH
and the gel time was determined by measuring the and so the exotherm curve provides information on the
resistance to the motion of an 8 mm diameter glass extent of cure in the resin during the polymerization.
tube probe using a Tecam gel-time meter (Townson
and Mercer, Australia). At the same time, the cure
exotherm was measured by placing a thermocouple in RESULTS AND DISCUSSION
the centre of a 30 ml quantity of the catalysed resin Effect of inhibitor level
contained within a glass test-tube (19 mm diame- The important role played by the initiator on the
ter  150 mm long) and initially maintained at 25 C. curing behaviour of the polyester resin is illustrated in
The tube and contents were then immediately Figs 2 and 3. During a typical reaction there is a
transferred to an air-bath jacketted by a 25 C water- induction period in which polymerization is initially
bath and the temperature rise due to the polymeriza- inhibited, but as time proceeds the reaction accelerates
tion was recorded electronically. The exotherm rise and the temperature rises to a maximum. In the

Figure 1. Typical structures of the


resin, initiators and inhibitor.

130 Polym Int 50:129134 (2001)


Cure of unsaturated polyester resins

3, leads to depletion of the initiator before polymer-


ization is complete. This phenomenon is analogous to
the dead-end polymerization discussed by O'Driscoll
and McArdle.18
The role of the inhibitor can best be described in
terms of the initiation kinetics. It is generally con-
sidered2 that Co2/Co3 ions reduce/oxidize hydro-
peroxides, leading to the formation of free radicals and
the consequent regeneration of the Co2 species
during the reaction
kd1 .
R OOH Co2 ! RO OH Co3 3
kd2 .
R OOH Co3 ! ROO H Co2 4

Presumably, a similar process applies to the interaction


Figure 2. Measured and corrected exotherm of the unsaturated polyester of Co2/Co3 ions with peroxides; however, the exact
mechanism is not clear. Beaunez et al 19 have noted
resin containing 0.2 wt% cobalt octoate solution, 1 wt% AAP and varying
amounts of TBC solution. The arrows indicate the corresponding gel times.
.
that the alkoxy radical (RO ) formed in eqn (3) is
much more reactive to ethylenic monomers than the
peroxy radical (formed in eqn (4) and so eqn (3)
measured exotherm data, the temperature then determines the rate of initiation. Equation (4) is
decreases due to heat loss to the environment: this important, however, because in this step Co2 is
stage is virtually eliminated in the heat-loss corrected regenerated, which results in a pseudo-steady-state for
exotherm curves which allow for this effect. As the the Co2 concentration. Assuming that the rate of
level of inhibitor is raised, Figs 2 and 3 reveal that the consumption and regeneration of the Co2 ions are
induction time is increased. A comparison of these approximately equal (ie a steady-state concentration of
data with the gel times measured with the gel-time Co2 is attained) the rate of formation of alkoxy
meter shows that, in general, the induction period radicals can be shown6 to be
corresponds closely to the gel point, as is observed in kd1 kd2 ROOHCo2 0
the data of Thomas et al. 7 This correlation is in Ri 5
kd1 kd2
agreement with the commonly held view5,6,16,17 that
the gel point occurs at a low degree of reaction in kd ROOHCo2 0
multifunctional chain growth polymerization, pro-
vided that the kinetic chain length is long. The As a result, the rate of radical production is predicted
maximum exotherm is also affected by the TBC to be approximately constant unless the peroxide
concentration, and the corrected exotherm tempera- concentration is severely depleted, as noted above.
ture decreases at high TBC levels. It appears that the When coupled with the idealized expression for the
addition of excessive levels of inhibitor (above 0.1 wt% rate of free radical polymerization,20 this gives the rate
TBC), particularly for the MEKP system shown in Fig of polymerization as
1=2
dM kp Mfkd 1=2 ROOH1=2 Co2 0
6
dt 1=2
kt
To improve storage life and for ease of application,
resin systems contain varying levels of inhibitor (X)
whose purpose is to consume adventitious radicals
.
(R ), such as alkoxy or peroxy species, during storage
and react with radicals formed in the early stages of
processing, as shown by the reaction
. kx .
R X ! RX 7
.
where RX is assumed to be an inactive radical, and k x
is the rate of inhibition. If the inhibitor is efcient (ie
the rate of inhibition is fast compared with the rate of
radical production) and the loss of radicals by bi-
molecular termination can be ignored, then radicals
Figure 3. Measured and corrected exotherm of the unsaturated polyester produced by the mechanism in eqns (3) and (4) will be
resin containing 0.2 wt% cobalt octoate, 1 wt% MEKP and varying amounts almost immediately consumed by inhibitor (eqn (7))
of TBC solution. The arrows indicate the corresponding gel times. and a steady-state concentration of radicals will exist.

Polym Int 50:129134 (2001) 131


WD Cook et al

Thus the rate of change in radical concentration will be


dR . .
kd ROOHCo2 kx R X 0 8
dt
and so

. kd ROOHCo2
R 9
kx X
Thus the rate of loss of inhibitor, as shown by the
reaction in eqn (7), is given by4,21
dX .
kx R X
dt
kd ROOHCo2 10
Figure 5. Measured and corrected exotherms of the unsaturated polyester
When the inhibitor is nally consumed, the polymer- resin containing 0.2 wt% cobalt octoate solution, a constant (undisclosed)
ization reaction can commence. Thus the induction, as concentration of TBC solution and varying amounts of MEKP.
shown in the initial stages of the exotherm curves in
Figs 2 and 3, is controlled by this inhibition reaction.
For an isothermal polymerization (which applies to the linear with the inhibitor concentration as predicted by
early stages of the experiment) and assuming that the eqn (12). Previous rheology and DSC investigations of
initiator is not signicantly depleted, eqn (10) shows unsaturated polyesters11,12 and styrene/divinyl ben-
that the inhibitor concentration will decrease with zene13 showed a similar trend for the gel time or for the
time, according to4,21 reaction induction time. It is interesting to note that
the gel time is not zero when the concentration of
X X0 kd ROOHCo2 t 11 added inhibitor is zero, and that when the gel time is
extrapolated to zero, the intercept on the abscissa is
where [X]0 is the initial concentration of inhibitor. For negative. This intercept is consistent with the presence
active scavengers, the polymerization is effectively of inhibitor added to the resin during its production in
delayed until [X] approaches zero.4,21 Therefore, from the plant, and from eqn (12) the magnitude of this
eqn (11) the polymerization induction time is given by intercept can be interpreted as the effective concentra-
X0 tion of pre-existing inhibitor.
tx 12 The effect of varying the level of MEKP on the
kd ROOHCo2
exotherm behaviour is shown in Fig 5. At low con-
This equation is similar to that derived by other centrations of MEKP, the induction period is long and
workers1113 but it specically includes the concentra- the exotherm is low. This suggests that the initiator
tions of the three main speciesinhibitor, initiator and may be partially depleted before full reaction. When
accelerator. the MEKP level is increased, the exotherm rises to a
The dependence of the gel point on the inhibitor plateau value and the induction time is progressively
level is shown in Fig 4. At low concentrations of reduced. Similar behaviour is also observed for the
inhibitor, the gel time appears to be approximately AAP system (Fig 6). The acceleration of the reaction

Figure 4. Dependence of gel time on TBC concentration for unsaturated Figure 6. Measured and corrected exotherm of the unsaturated polyester
polyester resin initiated with 0.2 wt% Co octoate and either 1 wt% AAP (&) resin containing 0.2 wt% cobalt octoate solution, a constant (undisclosed)
or 1 wt% MEKP (*). concentration of TBC solution and varying amounts of AAP.

132 Polym Int 50:129134 (2001)


Cure of unsaturated polyester resins

Figure 9. Measured and corrected exotherm of the unsaturated polyester


resin containing 1.0 wt% AAP, a constant (undisclosed) concentration of
Figure 7. Reciprocal gel time versus the concentration of AAP (&) or TBC solution and varying amounts of cobalt octoate solution.
MEKP (&) added to the polyester resin catalysed with 0.2 wt% cobalt
octoate solution. The lines are guides to the data.

by increased levels of peroxide is conrmed by the gel- between the gel time and cobalt octoate at low
time results shown in Fig 7. As predicted by eqn (12), accelerator concentrations.
the gel time is reciprocally related to the initiator It is interesting to note that, for both the MEKP and
concentration over most of the initiator range inves- AAP initiated systems, the gel time extrapolates to a
tigated, which is consistent with the rheology and DSC nite value at zero concentration of added cobalt salt
studies of other workers.1113 (see Fig 10), which may result from self-decomposi-
A similar accelerating effect of the cobalt octoate tion of the peroxide or by the accelerating decomposi-
accelerator is shown for the exotherm data in Fig 8 and tion of the peroxide by catalytic impurities in the resin,
9. Decreasing concentrations of cobalt salt extend the in agreement with other workers.11 For the AAP
induction time and slows the reaction. It is interesting system, the measured gel time is longer than that
to note that in contrast to the results for varying expected from the extrapolated value at high levels of
peroxide, the corrected exotherm is independent of the Co2. This may be caused by side reactions such as
cobalt salt level, suggesting that `full reaction' occurs reduction of the propagating radicals or the alkoxide
even at very low rates of initiation because the Co2 radicals by Co2, as has been suggested elsewhere.6,19
species is not consumed in the reaction but is
regenerated as shown in eqn (4). The plot of the gel-
time data according to eqn (12) is shown in Fig 10. At CONCLUSIONS
low concentrations of cobalt, an approximately linear The gelation and exotherm behaviour of an unsatu-
relation is exhibited between the reciprocal of the gel rated polyester resin with varying levels of MEKP
time and the cobalt concentration. Rheological studies initiator, cobalt octoate and TBC were studied. The
by Yang and Suspene11 on styreneunsaturated poly- gelation point has been found to correspond with the
ester systems showed an analogous relationship onset of the polymerization as expected for network

Figure 8. Measured and corrected exotherm of the unsaturated polyester Figure 10. Reciprocal gel time versus the concentration of cobalt octoate
resin containing 1.0 wt% MEKP, a constant (undisclosed) concentration of solution added to the polyester resin initiated with either AAP (&) or MEKP
TBC solution and varying amounts of cobalt octoate solution. (*). The lines are guides to the data.

Polym Int 50:129134 (2001) 133


WD Cook et al

formation via chain-growth polymerization. The gel 5 de la Cuba K, Guerrero P, Eceizal A and Mondragon I, Polymer
time was found to be proportional to the inhibitor 37:275 (1996).
6 Cook WD, Simon GP, Burchill PJ, Lau M and Fitch TJ, J Appl
concentration and was inversely related to the con- Polym Sci 64:769781 (1997).
centrations of peroxide and cobalt salt accelerator, as 7 Thomas A, Jacyszyn O, Schmitt W and Kolczynski J, in Pro-
predicted by theory. The exotherm data obtained from ceedings of 32nd Annual Technical Conference, Reinforced
curing under adiabatic conditions were consistent with Plastics/Composites Institute, Section 3-B, Society of Plastics
these conclusions and complement previous work Industry (1977).
8 Grentzer TH, Rust DA, Lo SK, Spencer CJ and Hackworth
utilizing different experimental techniques.1113
GW, in Proceedings of 46th Annual Conference, Composites
Institute, Section 1-B, Society of Plastics Industry (1991).
9 Salla JM, Ramis X, Martin JL and Cadenato A, Thermochim Acta
ACKNOWLEDGEMENTS 134:261 (1988).
10 Cassoni JP, Harpell GA, Wang PC and Zupa AH, in Proceed-
The authors would like to thank Dr John Forsythe, Dr
ings of 32nd Annual Technical Conference, Reinforced
Ference Cser, Dr Alex Kootsookos, Dr Peter Burchill, Plastics/Composites Institute, Section 3-E, Society of Plastics
Dr Graham Durrant and Mr Enzo Palma for their Industry, (1977).
helpful discussions, and Huntsman Chemical Co 11 Yang Y-S and Suspene L, Polym Eng Sci 31:321 (1991).
Australia Pty Ltd for the provision of materials. 12 Ramis X and Salla JM, Polymer 36:3511 (1995).
13 Batch GL and Macosko CW, J Appl Polym Sci 44:1711 (1992).
14 Salla JM and Martin JL, J Therm Anal 42:1025 (1994).
15 Rojas AJ, Borrajo J and Williams RJJ, Polym Eng Sci 21:1122
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134 Polym Int 50:129134 (2001)

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