Thermochimica Acta 374 (2001) 159±169

Kinetics of Alder-ene reaction of

Tris(2-allylphenoxy)triphenoxycyclotriphosphazene
and bismaleimides Ð a DSC study
M. Sunitha, C.P. Reghunadhan Nair*, K. Krishnan, K.N. Ninan
Propellant and Special Chemicals Group, Vikram Sarabhai Space Centre, Trivandrum-695022, India
Received 27 September 2000; received in revised form 12 March 2001; accepted 12 March 2001

Abstract

Tris(2-allylphenoxy)triphenoxycyclotriphosphazene was reacted with three bismaleimides (BMI), viz. bis(4-maleimido

phenyl)methane (BMM), bis(4-maleimido phenyl)ether (BME) and bis(4-maleimido phenyl)sulphone (BMS) via the Alder-
ene reaction. The differential scanning calorimetric analysis of the blend manifested two distinct exotherms. The low
temperature exothermic reaction was attributed to the Wagner-Jauregg reaction following the ene reaction and the strong
exotherms at around 250±2708C to the cross-linking Diels±Alder reactions of the initially formed adducts. The Kinetic
parameters, viz. activation energy (E) and pre-exponential factor (A) of the reactions were evaluated by Kissinger and Ozawa
methods using the variable heating rate method. The kinetic data revealed that the Wagner-Jauregg reaction was disfavoured
by electron-withdrawing nature of the BMI. The Diels±Alder reaction was facilitated by the electron-withdrawing nature of
the bismaleimide. The activation energy for the ®rst exothermic stage decreased and for the second major step increased on
enhancing the stoichiometry of BMI in the blend for a given pair. The activation parameters served to predict the isothermal
cure pro®les of the blends and deduce the possible network structure under the given conditions of cure temperature and
stoichiometry. # 2001 Elsevier Science B.V. All rights reserved.

Keywords: Cyclotriphosphazene; Bismaleimides; Alder-ene reaction; Thermal polymerisation; DSC kinetics

1. Introduction addition-cure formulations, based on co-reaction of

bisallyl phenols and bismaleimides are the leading
Despite the good attributes of processability and ones among tough matrices of carbon composite for
thermo-mechanical pro®le, the dominance of BMI advanced aerospace applications [8±10]. Maleimide
systems in high performance composites for aerospace reacts with allyl phenols through the Alder-ene reac-
industry has been partially hampered by the inherent tion via an intermediate Wagner-Jauregg reaction
brittleness of the system [1±4]. A recent development [10,12]. The reaction mechanism and product pro®les
in the toughening of BMI compositions is based on have been identi®ed by studies on model compounds
the reactive blends with allyl phenyl compounds, [12]. Alder-ene reactions of allyl phenyl derivatives
particularly diallyl bisphenols [5±7]. Commercial such as Tris(2-allylphenoxy)triazine with BMIs have
been used to derive thermosetting formulations [13].
*
Corresponding author. Tel.: ‡91-471-415-236/56;
With a view to develop thermally stable formulations
fax: ‡91-47-564-777/5. based on cyclotriphosphazenes, we used the Alder-ene
E-mail address: [email protected] (C.P. Reghunadhan Nair). cure chemistry for designing the novel thermosets [14].

0040-6031/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 3 1 ( 0 1 ) 0 0 5 0 2 - 0
160 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169

The protocol was to design allyl phenoxy substituted Analyser system in conjunction with a TC-10ATA
cyclotriphosphazenes and effect their cure using processor and a standard DSC-20 apparatus. About
BMIs. Phosphazene moiety is known to confer ther- 5 mg of the dry sample blend was weighed and
mal and ¯ame retardancy to polymer systems [15±17]. encapsulated in 40 ml Al cups with a pierced lid
The kinetics of Alder-ene reaction has not been and was used for DSC analysis. The temperature
reported. In this work, we report the kinetic analyses and heat ¯ow calibrations were done by the recom-
of Alder-ene reaction between Tris(2-allylphenoxy)- mended procedure using pure indium metal of melting
triphenoxycyclotriphosphazene and various BMIs point 156.68C and heat of fusion, DH f ˆ 28:45J/g.
using DSC technique. Differential scanning calorime- The peak temperature of all the samples were deter-
try (DSC) has been extensively used to determine the mined from the DSC curves by area integration of
enthalpy and kinetics of the exothermic reactions of the exotherm and ®nding the point at which @H/@T is
thermosetting polymers [27,28]. The Arrhenius acti- null, with the help of dedicated software. When the
vation parameters of different steps of reaction and peaks were not well resolved, experiments were
their dependency on reactant stoichiometry and struc- repeated with varied quantities of the resin till de®ned
ture of BMIs have been examined. maxima were obtained. In case the peak was ill
de®ned or partly merged with another one, manual
deconvolution was done to de®ne the peak, and peak
2. Experimental maximum was measured manually from the tempera-
ture±heat ¯ow curve. This was associated with some
2.1. Materials error, re¯ected as proportionate standard deviations in
the derived parameters.
Bis(4-maleimido phenyl)methane (BMM), bis(4-
maleimido phenyl)ether (BME), bis(4-maleimido
phenyl)sulphone (BMS) were synthesised by standard 3. Results and discussion
procedure as described elsewhere [25]. Tris(2-allyl
phenoxy)triphenoxycyclotriphosphazene (APCP) was 3.1. Synthesis of APCP
synthesised from hexachlorocyclotriphosphazene
(HCP) and phenol and 2-allyl phenol by a method APCP was synthesized from HCP by reacting it
being published [14]. APCP is a mixture of bis-, Tris- with three equivalents of sodium phenolate followed
and tetrakis-allyl phenoxy substituted compounds in a by excess of sodium (2-allyl phenolate). The inter-
proportion corresponding to an over all composition of mediate triphenoxy trichlorocyclotriphosphazene was
Tris(allyl phenoxy) derivative, as con®rmed from 31 P- analyzed for product distribution by GPC and
NMR, 1 H-NMR and elemental analyses. The propor- 31
P-NMR. High resolution by GPC showed APCP to
tion of Tris compound is approximately 63% (com- be essentially a mixture of three components. 31 P-NMR
puted from 31 P-NMR). Acetone was distilled from dry con®rmed this observation. The NMR spectrum
potassium carbonate. shown in Fig. 1 indicates that the product is a mixture
of di(phenoxy)tetrachlorocyclotriphosphazene, sym-
2.1.1. Blending metrical tri(phenoxy)-tri(chloro)cyclotriphosphazene,
APCP and the BMI of stoichiometric ratios 1:1, assymmetrical tri(phenoxy)-tri(chloro)cyclotriphos-
1:1.5 and 1:2 were weighed and dissolved in acetone. phazene, tetra(phenoxy)-di(chloro)cyclotriphospha-
The solvent was evaporated in vacuum and the result- zene and penta(phenoxy)monochlorocyclotriphospha-
ing mixture was dried in vacuum at 508C for 8 h. zene. The assignment of the spectrum and relative mole
fractionofallcomponentsaregiveninTable1.Theoverall
2.2. Instrumental degreeofsubstitutionoftheintermediatewasestimatedto
be2.85,onneglectingtheextremelysmallconcentrations
2.2.1. DSC of higher substitution compounds accounting for the
DSC experiments were performed at varying heat- remaining fractionalsubstitutionof0.15. Onsubstituting
ing rates in static air using a Mettler TA 3000 Thermal the remaining chlorine atoms of this intermediate with
 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169 161

Proton NMR of APCP (CDCl3); d (ppm): 6.75±7.25

(m, 9H, aromatic), 5.75±6.1 (m, 1H, =CH allyl), 4.75±
5.25 (m, 2H, =CH2) and at 3.3±3.4 (d, 2H, ±CH2).
Thus, based on the product distribution of the
intermediate which has been completely substituted
to derive the end product, APCP consists of essentially
four components as detailed in Table 1. The overall
composition corresponds to three phenoxy and three
allylphenoxy groups substituted on HCP. The ideal
structure of APCP is depicted in Scheme 1.

3.2. DSC analyses

The non-isothermal DSCs of representative blends

of APCP with three bismaleimides are shown in Fig. 2.
On heating, the BMI and the blends undergo melting
(Fig. 2). In cases of BMM and BME dual melting
peaks were observed. The melting ranges are from 130
to 1908C depending on the nature of the blend and
heating rate employed and increasing in the order
BMM > BME > BMS. The melting is followed by
two exotherms, which are overlapping in nature. Allyl
Fig. 1. 31 P-NMR spectrum of the intermediate Ð tri(chloro)- phenyl derivatives are known to react with BMI by a
tri(phenoxy)cyclotriphosphazene. sequence of reactions comprising of ene, Wagner-
Jauregg and Diels±Alder reactions, collectively
known as Alder-ene reaction [10,12]. The accepted
reaction sequences for an ideal blend are shown in
sodium (2-allylphenolate), a mixture of products as Scheme 2. Previous DSC analyses of similar reactive
detailed in Table 1 was obtained. The ®nal product con- blends have revealed the existence of two or three
tains on the average three phenoxy groups and three distinct exotherms in league with the Alder-ene reac-
allylphenoxy groups (as per NMR). The relative ratio tion sequences [18,19]. Accordingly, the ene reaction
ofphenolandallylphenolwasascertainedfromtheproton occurs at 100±1908C. Since this coincides with the
NMR of the ®nal product. The NMR assignments are melting endotherm, corresponding exotherms could
given below. barely be differentiated to facilitate a comparison and

Table 1
Characteristics of the components of APCP
31
Component in P chemical shifts, signal nature, Mole fraction Contribution towards Product after
intermediate integrationa functionality of substitution
intermediate by allylphenol
PCl2 P(OPh)Cl P(OPh)2

Diphenoxy 4.38 (t) 19.27 (d) ± 28.32 0.58 Tetrakis allyl

Symmetrical triphenoxy ± 17.14 (d) ± 5.01 1.51 Symmetrical Trisallyl
Asymmetrical triphenoxy 3.06 (dd) 14.7 (dd) 23.92 (dd) 15.43 0.46 Asymmetrical Trisallyl
Tetraphenoxy ± 21.75 (d) 24.44 (t) 2.81 0.12 Bisallyl
Pentaphenoxy ± 19.2 (t) 25.3 (d) 33.4 0.17 Monoallyl
a
(s) Singlet; (d) doublet; (t) triplet; (dd) doublet of a doublet.
162 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169

Scheme 1. Synthesis of APCP.

kinetic calculation. The ®rst exotherm (190±2158C) in lead to any signi®cant variation in the reactivity of the
the present case can therefore be attributed to the allyl phenoxy groups located on different phospha-
Wagner-Jauregg step and the second to the extended zene rings. Throughout the work, the same composi-
Diels±Alder reaction and polymerisation of the tion was used to study kinetics of reactions of blends
unreacted monomers if any. with different BMIs to avoid errors arising out of
Although APCP is a mixture of cyclotriphospha- variation in distribution of the components of the
zene of varying degree of substitution of the functional mixture.
group (i.e. allyl phenoxy), the component molecules APCP was blended with three BMIs, viz. BMM,
have practically the same size and molar masses. The BME and BMS in the ratio 1:2.0. In the case of
difference in substitution pattern is not expected to BMM, three different stoichiometric compositions,

Fig. 2. DSC curves of BMI/APCP systems: (- - -) BMM (1:1.5); (


) BME (1:2); (Ð) BMS (1:2). Heating rates: 78C/min for BMM and
BME; 108C/min for BMS.
 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169 163

Scheme 2. Sequences of Alder-ene reaction.

viz. 1.1, 1:1.5, 1:2.0 were used. The DSC data are identical temperature pro®le for the second major
compiled in Table 2. The Tm1 and Tm2 represent the step, although BMM exhibited slightly higher tem-
peak maximum temperatures for Wagner-Jauregg and perature in comparison to the other two. Increasing
Diels±Alder reactions, respectively. The Tm values BMI stoichiometry marginally shifted the cure
for the W-J reaction were lower for BMM in com- maximum to higher temperature regime, in the case
parison to BME. All the three systems exhibited nearly of BMM.

Table 2
DSC peak maximum temperatures at different heating rates for polymer blends

Heating rate, BMM (1:1) BMM (1:1.5) BMM (1:2) BME (1:2) BMS (1:2)
F (8C/min)
Tm1 Tm2 Tm1 Tm2 Tm1 Tm2 Tm1 Tm2 Tm1 Tm2

2 ± ± 179 221 170 242 190 225 190 208

5 195 243 189 242 197 255 200 250 198 245
7 204 249 205 251 200 263 212 256 200 259
10 205 257 211 257 223 272 217 265 206 266
15 220 267 220 270 224 280 230 276 210 277
164 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169

3.3. Kinetic analysis

The kinetic analyses of the two steps were done

by the variable heating rate method based on the
methods of Kissinger [20] and Ozawa [21±23].
Recently, a similar approach was used to study the
kinetics of Claisen rearrangement of diallyloxy
bisphenols [24].
The peak maxima (Tm) for two stages of reactions
and for various stoichiometric combinations obtained
from DSC analysis are given in Table 2. The values
showed a regular increase with increase in heating
rate. The non-isothermal integral methods were not
employed for the kinetic analyses because the exother-
mic reactions, particularly the low temperature ones,
are not resolved and hence not amenable for area Fig. 3. Kinetic plots by Kissinger method.
integration. Instead, the two well-known methods,
viz. Kissinger and Ozawa methods based on variable The theoretical slope (D) of the above equation is
heating rate which depend on peak maxima in DSC 1 2=x ‡ 1=…1 ‡ x† 1=…x ‡ 3†. The process of
were employed for the purpose, where the apparent iteration was continued to get a constant value for
variations in activation energy caused by heating rates E ˆ 2:303  slope…exp†=D. This re®nement is
are also taken care of. Moreover, these methods do not recommended for Ozawa method in ASTM E 698
invoke reaction order n or fractional conversion a in [30]. Typical kinetic plots by Kissinger and Ozawa
deriving the kinetic parameters. The ®nal forms of methods are shown in Figs. 3 and 4, respectively.
Kissinger [20] and Ozawa [21±23] equations, used for A was found in both cases from the relation
®nding the activation parameters are given below.
Kissinger equation: fE eE=RTm
Aˆ (4)
RTm2
2:303 d‰log…f=Tm2 †Š E
ˆ (1) The computed activation parameters are given in
d…1=Tm † R Table 3 for all the blend compositions and for two
where Tm is the temperature corresponding to the
maximum in the DSC exotherm at a heating rate f.
From the slope of the linear plot of log…f=Tm2 †
against 1/Tm, E can be calculated.
Ozawa equation:
2:15 d‰log…f†Š E
ˆ (2)
d…1=Tm † R
where E was obtained from the slope of the plot of log
f against 1/Tm.
The E-values obtained by Ozawa method needed
re®nement by iteration. This was done based on a two-
term approximation for the Arrhenius temperature
[29]
 
x …x ‡ 1† E
P…x† ˆ e ; where x ˆ (3)
…x ‡ 3† RT Fig. 4. Kinetic plots by Ozawa method.
 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169 165

Table 3
Kinetic parameters for different reactions

System Reaction step Kissinger Ozawa E (kJ/mol) for

1 1
homopolymerisation [25]
E (kJ/mol) A (s ) E (kJ/mol) A (s )

BMM (1:2) I 54.6  7.1 3.62  103 54.9  7.1 4.02  103 76.9
II 113.5  8.9 6.47  108 113.7  8.9 6.88  108
BMM (1:1.5) I 75.3  10.4 7.81  105 75.5  10.4 6.42  105
II 84.3  2.5 1.09  106 84.7  2.5 1.21  106
BMM (1:1) I 75.9  17.0 1.31  106 76.3  17.0 1.52  106
II 96.3  4.5 2.15  107 94.3  4.4 1.88  107
BME (1:2) I 85.9  11.3 9.15  106 86.2  11.3 9.81  106 119.6
II 81.7  3.4 4.83  105 82.0  3.4 5.14  105
BMS (1:2) I 175.7  13.2 2.78  1017 175.85  6.1 2.9  1017
II 53.3  13.2 4.51  102 53.5  6.2 4.75  102

reaction steps. Both the methods give nearly identical exotherm is not due to the thermal homopolymerisa-
values for a given reaction. tions of BMIs, the probability for which is less,
particularly when the BMI is stoichiometrically de®-
3.4. Reaction mechanism cient in the blend.
Both reaction steps were identi®ed for all the
A close examination of the DSC results and kinetic stoichiometry. This implies that all the sequences in
data showed that the Wagner-Jauregg reaction, essen- the Alder-ene reactions could occur parallely when the
tially involving the Diels±Alder addition of BMI to the system is heated dynamically, or at a stretch at high
ene adduct showed a strong dependency on the elec- temperature. Thus, the network structure could depend
tron density of the BMI. The electron-de®cient BMS upon the heating schedule and the stoichiometry. The
was found to have signi®cantly higher activation for reaction sequences in an ideal case of blend is shown
this reaction. However, it can be concluded that this in Scheme 2.
step which is known to be reversible [13], is facilitated
by electron density of the p-bond of BMI. On the other 3.5. Effect of stoichiometry
hand, the second major polymerisation step involving
the Diels±Alder addition of BMI to the initially The effect of stoichiometry of BMI ‡ APCP on the
formed Wagner-Jauregg adduct was facilitated by phenomenological and kinetic aspects of the reaction
the electrophilicity of the dienophile. Thus the trend was studied by preparing a typical blend of
in activation energy, BMS < BME < BMM is strictly BMI ‡ APCP in the ratio 1:1, 1:1.5 and 1:2.
in accordance with the decreasing electrophilicity of It is reported that optimum stoichiometry for allyl-
the double bond of BMI. bismaleimide reaction is 1:3 [9±12]. However in most
It is known that Diels±Alder reaction is facilitated of the cases, a lower stoichiometry of the BMI is
by the increased electrophilicity of the dienophile. preferred in order to reduce the cross-link density of
Since a reverse trend was observed for the Wagner- the network. In the present study also, the stoichio-
Jauregg reaction, it may be concluded that this reac- metry of BMI was kept to a maximum of 1:2. This
tion may be following a mechanism different from the could also avoid the possible contribution of the
conventional Diels±Alder reaction although the ®nal homopolymerisation of BMI at higher temperature
product looks like a Diels±Alder adduct. The E-values and minimise the effect of its contribution in the
for the second step are different from those reported present kinetic evaluation. The activation parameters
for the thermal homopolymerisation of the BMIs, for the two steps for three different stoichiometries
estimated by Rogers method [25], which are given were calculated and their values are also included in
in Table 3 for BMM and BME. This indicates that this Table 3. The activation parameters are normally
166 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169

expected to be independent of stoichiometry and the bismaleimides and for different stoichiometries for
trend is followed up to a BMM stoichiometry of 1:1.5. BMM ‡ APCP. The reaction order, n was found from
However, the blend composition (1:2) showed large the Coats±Redfern treatment [26] for the second step
variation in E and A values of both the stages of using the relationship
reactions. When BMM stoichiometry is enhanced  
to 1:2, the Wagner-Jauregg reaction is found to be g…a† E
ln ˆ lnf…AR=fE†…1 2RT=E†g (6)
facilitated while the high temperature cure requires T2 RT
higher activation. This may also be due to probable
changes in reaction mechanism at higher BMI- where
content. The enhanced activation energy for the ( )
Diels±Alder reaction may be attributed to the effect 1 …1 a†1 n
g…a† ˆ for n 6ˆ 1
of diffusion control in the kinetics of this cross-linking …1 n†
step, as the concentration of the cross-linking agent
(BMI) is increased in the blend. and when
The kinetic parameters derived form the present n ˆ 1; g…a† ˆ ln…1 a† (7)
DSC study has been particularly used to compare the
relative reactivities of different reaction steps of APCP where a was obtained by integration of the 2nd
with various BMIs under identical reaction conditions. exotherm in typical cases, where the baseline is
In these perspectives, the derived kinetic parameters unambiguous. a ˆ Ha =Ht , where Ha is the fractional
are useful and make sense. The kinetic parameters enthalpy and Ht the functional enthalpy.
from DSC for solid state reactions may not make sense The plot of ln‰…g…a†=T 2 †Š for various assumed
to de®ne the absolute reactivity, etc. as normally values of n ranging from 1±2.5, against reciprocal
inferred from normal reaction kinetics in closely of absolute temperature (T) was performed. The cor-
de®ned systems. However, the derived kinetic para- relation coef®cient (r), for the linear ®t for different
meters can be correlated to the reactivities particularly values of n are given in Table 4.
in temperature regimes, where the reactants retain In nearly all cases, the best value of n was found to
their liquid consistency or are suf®ciently mobile in be 2. Using this value of n ˆ 2, a was calculated from
order not to invoke the phenomena such as diffusion, the computed fractional enthalpy at each temperature
etc. The kinetic parameters derived from the solid state T. The Coats±Redfern plot is shown for a typical case
reactions such as the later part of the Diels±Alder in Fig. 5.
reaction, at best have only empirical signi®cance and
are useful for comparing reactivities and for predicting Table 4
the isothermal cure pro®les at a given temperature. Determination of reaction order for the Diels±Alder reaction step
for reaction of APCP/BMM (1:1.5), APCP/BME (1:2) and APCP/
3.6. Prediction of Isothermal cure pro®le BMS (1:2) at a heating rate of 78C/min by Coats±Redfern method
and network structure BMI system Reaction Correlation
order (n) coefficient (r)
The kinetic modeling is generally used for the cure BMM 1 0.9410
time±temperature prediction of polymer systems. 1.5 0.9720
The equation relating time, temperature and frac- 2 0.9810
tional conversion for any step is given as 2.5 0.9760
BME 1 0.9607
E=RT† 1=1 n
aˆ1 f1 A…1 n†t e… g (5) 1.5 0.9800
2 0.9799
where a is the fractional conversion, A the pre-expo- 2.5 0.9674
nential factor, n the order of the reaction, t the time, E BMS 1 0.9550
the apparent activation energy and T the temperature. 1.5 0.9780
Isothermal cure for the Diels±Alder reaction was 2 0.9803
2.5 0.9704
calculated using the above equation for the three
 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169 167

Fig. 5. Coats±Redfern kinetic plot for determination of reaction Fig. 6. Isothermal time-conversion data for the cross-linking reaction
order for APCP/BMM for 1:1.5 blend. of the three reaction systems: BMM, BME, and BMS at 2508C.

Usually, Alder-ene adducts are cured by heating at the preceding ene and Wagner-Jauregg reaction will
2508C. Heating is done stage-wise. The time-conversion be occurring at a comparatively faster rate.
data calculated for the ®nal cross-linking reaction for Since the cure reaction involves at least three major
the three reaction systems, viz. BMM, BME and BMS steps, the network structure could depend upon the
and for BMM at different stoichiometric ratios at cure temperature and on the stoichiometry. At a given
2508C are shown in Figs. 6 and 7, respectively. The temperature, all the three reactions are possible as
cure is practically completed in about 2 h at 2508C. evident from the DSC pro®le. The kinetics of each step
The difference among the various systems in cure be- is decided by its respective activation parameters and
haviour is not signi®cant. Comparison has been made reactant concentration. For example, at low cure tem-
for the ®nal cure step only, since at this temperature perature and at low concentration of maleimide, the

Fig. 7. Time-conversion pro®le for the cross-linking reaction of BMM at different stoichiometric ratios at 2508C.
168 M. Sunitha et al. / Thermochimica Acta 374 (2001) 159±169

cross-linked structure would be con®ned to the ene- 4. Conclusion

adduct or to the Wagner-Jauregg adduct. At higher
cure temperature, all the reactions are possible irre- Tris(2-allylphenoxy)triphenoxycyclotriphosphazene
spective of stoichiometry. Calculation of the relative was reacted with bis(4-maleimido phenyl)methane
reaction rate (from the activation parameters) could (BMM), bis(4-maleimido phenyl)ether (BME) and
lead to a ®rst approximation of the network structure. bis(4-maleimido phenyl)sulphone (BMS) via the
In majority of the cases, the cure is effected at Alder-ene reaction. The DSC of the blend manifested
2508C. It can be assumed that the ene reaction pre- two major exotherms. The low enthalpy reaction at
cedes at a suf®ciently faster rate at this temperature (in low temperature was attributed to the Wagner-Jauregg
comparison to the Wagner-Jauregg and Diels±Alder reaction following the ene addition and the strong
reactions). For a 1:2 stoichiometry, one equivalent of exotherm at around 250±2708C was caused by Diels±
the remaining bismaleimide can be considered to be Alder reactions of the initially formed adduct with
distributed between the Wagner-Jauregg and Diels± BMI. The kinetics of the reaction, followed by non-
Alder reactions. Since Diels±Alder reaction follows isothermal DSC using the variable heating rate meth-
Wagner-Jauregg reaction, the relative conversions in ods revealed that the Wagner-Jauregg reaction was
the two cases can be calculated to the ®rst approxima- disfavoured by electron withdrawing nature of the
tion, by assuming that at any time given, the product of BMI. The major cross-linking reaction was facilitated
Wagner-Jauregg reaction from the reactant for Diels± by the electron de®ciency of the BMI in league with
Alder reaction. Assuming that the Wagner-Jauregg the trend for Diels±Alder reaction. On increasing the
reaction is also second-order, the apparent relative BMI content beyond an allyl:BMI stoichiometry of
conversion can be calculated using Eq. (5). 1:1.5, an apparent change in reaction mechanism was
The conversion pro®le at three different cure tem- observed. The predicted isothermal cure pro®le shows
peratures for the typical case of BMM is shown in that the reaction is faster in the case of BMM and is
Fig. 8. It shows that at lower temperature, the Wagner- completed in 2 h at 2508C for all cases. Higher
Jauregg reaction dominates over the Diels±Alder reac- stoichiometry resulted in faster cure reaction. Predic-
tion and the network will be containing more of the tion of isothermal reaction pro®le for the two steps
structure resulting from the former. At higher cure shows that at lower cure temperature, the network is
temperature, the proportion of Diels±Alder structure mostly composed of structures resulting from Wagner-
increases in the network. Jauregg reaction. Diels±Alder structure dominates at
higher cure temperature.

Acknowledgements

The authors thank their colleagues in the Analytical

and Spectroscopy Division for the support in various
analyses. The permission granted by VSSC to publish
the results is gratefully acknowledged. M. Sunitha
thanks Indian Space Research Organisation for grant
of a fellowship.

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