Journal of Polymer Research 11: 181–187, 2004.

© 2004 Kluwer Academic Publishers. Printed in the Netherlands.

181

New Poly(Methacrylate)s Containing Benzylpiperazine and Methylpiperidine

Moieties

Cengiz Soykan1,∗ , İbrahim Erol2 , Hasan Türkmen3 and Yunus Akçamur1

1 Department of Chemistry, Yozgat Faculty of Science and Arts, University of Erciyes, Yozgat, Turkey
2 Department of Chemistry, Faculty of Science and Arts, University of Afyon Kocatepe, Afyon, Turkey
3 Department of Chemistry, Faculty of Science and Arts, University of Harran, Şanlıurfa, Turkey

(∗ Author for correspondence; Tel.: 0 354 242 1021; Fax: 0 354 242 1022;
E-mail: soykan@erciyes.edu.tr, soykancengiz@hotmail.com)

Received 13 October 2003; accepted in revised form 5 January 2004

Key words: 2-(4-benzyl piperazin-1-yl)-2-oksoethyl methacrylate, 2-(4-methylpiperidin-1-yl)-2-oksoethyl methacrylate,

activation energy, Ozawa method, radical polymerization

Abstract
The synthesis of two new methacrylate esters containing 2-(4-benzyl piperazin-1-yl)-2-oksoethyl and 2-(4-methylpiperidin-
1-yl)-2-oksoethyl group are described. The monomers produced from the reaction of corresponding 4-methylpiperidine-
chloroacetamide and 1-benzylpiperazinechloroacetamide with sodium methacrylate was polymerized in DMSO solution
at 65 ◦C using AIBN as an initiator. The monomers and their polymers were characterized by IR, 1 H- and 13 C-NMR
spectroscopy. The glass transition temperature of the polymers were investigated by DSC and the apparent thermal decom-
position activation energies (E d ) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance. By
using gel permeation chromatography, weight average (M w ) and number average (M n ) molecular weights and polidispersity,
indices of the polymers were determined.

Introduction exchange resin were discussed based on piperazine func-

Increasing interest in the development of speciality polymers
(functional polymers, polymer supports) in recent years has
led to a rich arsenal of methodologies and procedures for
the laboratory synthesis of functional monomers. More gen-
erally, however, (meth)acryloyl-based functional monomers
are more readily accessible, and hence more attractive for the
development of functional polymers for technological ap-
plications [1]. In particular, polymers of activated acrylates
and methacrylates are envisaged to play a major role in the
future development of functional and speciality polymers in
general. More specifically, the term “functional polymers” is
synonymous with “reactive polymers” and refers to insolu-
ble (crosslinked) beaded resins carrying chemically reactive
functional groups. In this sense [2], functional polymers are
employed as polymer supports and polymeric reagents for
a wide range of chemical and biochemical applications, in-
cluding chromatography [3, 4], peptide synthesis [5, 6] and
biochemical [7–9] and chemical [10, 11] catalysis.
It is well known from the literature that the compounds
containing amide moiety have a strong ability to form metal
complexes and exhibit a wide range of biological activities
[12–15]. We have synthesized two new methacrylate base
monomers which contain amide moiety. In earlier work [16]
kinetics of goldcyanide extraction using ion-exchange resins
containing piperazine functionality has been published. In
two previous papers [17, 18], the properties of a new ion-
tionality for goldcyanide extraction from cyanide solutions.
These studies show that the acid-base properties of the sec-
ondary amine groups of the piperazine polymeric ligand
were strongly modified when attached onto the PS-DVB
macroporous supports with an increase in the acidity prop-
erties of the piperazine group. However, the application of
these systems in industrial scale equipment using fixed col-
umn or fluidised bed technology requires knowledge of the
equilibrium and kinetics of the metal extraction processes
and the operating hydraulic behavior.
Thermogravimetric analysis (TGA) has been widely
used to investigate the decomposition characteristics of
many materials. Some methods have already been estab-
lished to evaluate the kinetic parameters from thermogravi-
metric data [19–27].
As far as we know, no reports have been observed in
the literature about the synthesis, polymerizations and use of
methacrylate esters having pendant 2-(4-methylpiperidin-1-
yl)-2-oksoethyl and 2-(4-benzylpiperazin-1-yl)-2-oksoethyl
moieties.
In this paper, the TGA technique is applied to 2-(4-
methylpiperidin-1-yl)-2-oksoethyl methacrylate and 2-(4-
benzylpiperazin-1-yl)-2-oksoethyl methacrylate homopoly-
mers. The apparent activation energy was evaluated by
isothermal thermogravimetric methods. The energies of
activation at different steps were calculated by Ozawa’s
method [19].
182
Experimental
Materials
4-methyl piperidine, 4-benzyl piperazine and chloroacetyl-
chloride (Merck) were used as received. Ethanol, methanol,
acetonitrile, chloroform, benzene, dichloromethane were
freshly distilled over molecular sieves prior to use. Formic
acid, n-heptane, diethylether, 1,4-dioxane, and sodium-
methacrylate (Aldrich) were used as received. 2,2’-Azobis-
isobutyronitrile (Aldrich) was recrystallized from chloro-
form and ethanol mixture and dried under vacuum for 24 h.
Measurements
A Fourier transform infrared (FTIR) spectrophotometer
from Jasco FTIR 460 plus was used to analyze the chemical
and/or physical interactions. 1 H- and 13 C-NMR spectra of
the monomers and polymers were recorded in CDCl3 with
tetramethylsilane as the internal standard using a Gemini
Varian 200 MHz NMR spectrometer. Thermogravimetric
data were obtained by using a Setaram DSC-131 instru-
ment and a Setaram labsys TGA thermobalance. Molecular
weight; (M w and M n ) of the polymer was determined us-
ing waters 410 gel permeation chromatography equipped
with a RI detector and calibrated with polystyrene standards.
The inherent viscosity of 1% (w/v) solution of polymer in
chloroform was determined at 25 ◦C using an automated
Ubbelohde viscometer.
Monomer Synthesis
Benzylpiperazinechloroacetamide (1) was prepared by re-
acting benzylpiperazine with chloroacetylchloride using the
(Et)3 N. 2-(4-benzyl piperazin-1-yl)-2-oksoethyl methacry-
late (BPOEMA) (2) was synthesized as follows: a mix-
ture of benzylpiperazinechloroacetamide (1 mol), sodium-
methacrylate (1.1 mol) in 100 ml acetonitrile and triethyl-
benzylammonium chloride (TEBAC) (0.1 mol) as a phase
transfer catalyst beter [28] and NaI (0.1 mol) as catalyst was
taken in a two-necked round-bottomed flask equipped with
a magnetic stirrer, thermometer, and heated to 80 ◦C. In a
reflux condenser in the presence of 100 ppm hydroquinone
as inhibitor. The reaction was continued for a further 24 h.
The reaction mixture was cooled to room temperature and
transferred to a separating funnel, washed sequentially with
distilled water, 5% NaOH solution and diethylether.
The organic layer was collected and dried over anhy-
drous MgSO4 overnight. Diethylether was evaporated and
the resulting monomer purified by recrystallization from
ethanol (yield 85%).
IR (neat), cm−1 : 1720, 1650 (C=O for ester and amide),
1630 (CH2 =C–),
1 H-NMR(δ, ppm from TMS in CDCl ): 7.2 (aromatic
3
ring protons, 5H); 5.8 (CH2 =, 1H); 6.2 (CH2 =, 1H); 4.8
(–OCH2 –, 2H); 3.7 (–CH2 , in piperazine ring); 3.3 (–CH2 ,
at benzyl ring, 2H); 1.9 (CH3 –, 3H).
13 C-NMR(δ, ppm from TMS in CDCl ): 164.2 (C=O
3
of amide); 168.8 (C=O of ester); 133.0 (=C); 127.1–138.4
C. Soykan et al.
(aromatic ring carbons); 124.1 (CH2 =); 71.1 (–OCH2 –);
63.0 (–CH2 , at benzyl ring); 44.4 and 55.9 (–CH2 , in
piperazine ring); 18.2 (CH3 ).
The esterification of sodium methacrylate with methylpi-
peridinechloroacetamide was also examined using TEBAC
under the same conditions and the monomers 2-(-4-methyl-
piperidin-1-yl)-2-oksoethylmethacrylate (MPOEMA) were
obtained.
IR (neat), cm−1 : 1720, 1650 (C=O for ester and amide),
1630 (CH2 =C–),
1 H-NMR(δ, ppm from TMS in CDCl ): 5.7 (CH =, 1H);
3 2
6.1 (CH2 =, 1H); 4.9 (–OCH2 –, 2H); 2.8 and 1.4 (–CH2 ,
in piperidine ring); 1.9 (CH3 , 3H, at piperidine ring); 1.8
(CH3 –, 3H).
13 C-NMR(δ, ppm from TMS in CDCl ): 168.9 (C=O of
3
amide); 170.4 (C=O of ester); 133.1 (=C); 124.4 (CH2 =);
71.8 (–OCH2 –); 33.8 and 43.1 (–CH2 , in piperidine ring);
22.0 (CH3 , at piperidine ring); 17.8 (CH3 ).
Polymerization
Polymerization of BPOEMA and MPOEMA was carried out
in glass ampoules under N2 atmosphere in dimethylsulphox-
ide solution with AIBN (1% based on the total weight of
monomers) as an initiator. The reacting components were
degassed by threefold freeze-thawing cycles and then im-
mersed in an oil bath at 65 ± 1 ◦ C for a given reaction time.
The polymers were separated by precipitation in diethylether
and reprecipitated from dichloromethane solution. The poly-
mers were finally dried under vacuum to constant weight at
room temperature and kept in a dessiccators under vacuum
until use.
Results and Discussion
As shown in Scheme 1, we propose a new route for new
methacrylate monomers.
The MPOEMA monomer was synthesized and charac-
terized by the same methods. The monomeric and polymeric
units are presented in Scheme 2.
Characterization of the Monomer and its Polymer
The 1 H-NMR spectrum of (BPOEMA), its polymer
poly(BPOEMA), and its attributions are shown in Fig-
ures 1a and b. The structure of BPOEMA and its polymer
poly(BPOEMA) are confirmed by 1 H-NMR spectral data.
The 13 C-NMR spectrum of MPOEMA and its polymer
poly(MPOEMA) are shown in Figures 2a and b. NMR
data were interpreted from the position of the formation
the different conformations and compared to those with the
structure of poly(MMA) prepared in similar conditions.The
NMR spectra of the polymer have the characteristic peake
of the polymeric units. Such as 2-(4-benzyl piperazin-1-
yl)-2-oksoethyl and 2-(4-methylpiperidin-1-yl)-2-oksoethyl
group. In methacrylate base group, the chemical assign-
ments of α-methyl and methylene protons and carbons are
shifted onto different chemical slides because of chemical
surroundings.
New Poly(Methacrylate)s Containing Benzylpiperazine and Methylpiperidine Moieties 183

Scheme 1.

Scheme 2.

The main evidence of the polymer formation is cer-
tainly the disappearance of some characteristic signals of
the double bond in the spectra and this fact was effectively
observed in our case. Thus, two bands vanished in the IR
spectrum: the absorption band at 920 cm−1 assigned to the
C–H bending of geminal =CH2 and the stretching vibration
band at C=C at 1630 crn−1 . From 1 H-NMR spectroscopy,
the formation of the polymer is also clearly evident from
the vanishing of the two singlets at 6.2 and 5.7 ppm of the
vinyl protons and the appearance of the broad signal at 1.5–
1.9 ppm assigned to an aliphatic –CH2 – group. All the other
spectroscopic signals for the macromolecule appeared in a
normal mode for the macromolecules.
and number average (M n ) molecular weights and the poly-
dispersity indexes (M w /M n ) of polymer samples are pre-
sented Table 1. The GPC traces showed a unimodel elu-
tion curves for both polymers (Figure 3). The molecular
weight of poly(BPOEMA) is somewhat higher than that of
poly(MPOEMA) with a polydispersity somewhat narrower
than that of poly(BPOEMA) due to prevention of BPOEMA
monomer transfer during purification through the chromato-
graphic column. The PDIs of the polymers are close to
2.0. The theoretical values of PDI for polymers via radical
recombination and disproportionation are 1.5–2.0, respec-
tively [29]. The value of PDI in homopolymerization is also
known to depend on chain termination.

Molecular Weights of the Polymers Determination of the Physical Parameters

The molecular weights of the polymers were determined Some physical parameters such as density (d), solubility
by GPC with polystyrene and tetrahydrofuran as the Stan- parameter (δ) and inherent viscosity (ηinh ) of the poly-
dard and solvent, respectively. The weight average (M w ) mers were determined in the study. The densities of the
184 C. Soykan et al.

polymers were determined experimentally by the flotation

method [30] at 25 ◦C using mixtures of methanol and formic
acid as the floating agent, and many glass beads of known
densities. The solubility parameters of the polymers were
determined by using a titration method [30] at 25 ◦ C from a
solubility test using CH2 Cl2 as solvent and n-heptane and
ethanol as non-solvent. Solutions of polymers in DMSO
at the concentration of 0.5 g dl−1 were used to determine
inherent viscosities (ηinh = ln ηr /C). Measurements were

Figure 2. Proton decoupled 13 C-NMR spectra of MPOEMA (a) and

poly(MPOEMA) (b).

Figure 3. The GPC traces of polymers.

Figure 1. 1 H-NMR Spectra of BPOEMA (a) and poly(BPOEMA) (b).

Table 1. Differantiel scanning calorimetry, molecular weight data and physical parameters of polymers

Sample Conv. (%) Tg ( ◦ C) Mw Mn M w /M n ηinh (dl g−1 ) δ (cal/cm3 )1/2 d (g cm−3 )

Poly(BPOEMA) 90 136 74000 38700 1.91 0.74 10.4 1.28

Poly(MPOEMA) 85 115 86200 47300 1.82 0.81 10.0 1.16
New Poly(Methacrylate)s Containing Benzylpiperazine and Methylpiperidine Moieties
performed by an Ubbelohde viscometer thermostatted at
25 ◦C. These values are shown in Table 1. The density
of poly(MPOEMA) is higher than that of poly(BPOEMA).
This result showed that poly(BPOEMA) chain stiffness, free
volume and induced better packing of polymer segments
is more than poly(MPOEMA) units. ηinh viscosity values
of poly(MPOEMA) is higher than that of poly(BPOEMA).
Because, molecular weight of poly(MPOEMA) is higher
than the poly(BPOEMA), for this reason the flow resistance
of the poly(MPOEMA) is greater than poly(BPOEMA).
The solubility parameter of poly(BPOEMA) is higher than
that of poly(MPOEMA). Because, the side groups of
poly(BPOEMA) are bigger and longer than that of the
poly(MPOEMA). For this reason the molecules of solvents
do not enter the polymer molecules and solubility becomes
difficult.
DSC Measurements
The glass transition (Tg ) temperatures were determined by a
Setaram 131 DSC. Samples of about 5–8 mg held in sealed
aluminum crucibles and the heating rate of 20 ◦C/min under
a dynamic nitrogen flow (5 l h−1 ) were used for the mea-
surements. From DSC measurements Tg was taken as the
midpoint of the transition region. These values are indicated
in Table 1. As shown in Table 1, the Tg of poly(MPOEMA)
was lower than that of poly(BPOEMA). This situation might
be attributable to bulky substituent groups; a polymer bear-
ing bulky side groups generally has a high glass transition
temperature, because for such a chain the moving segment is
necessarily large. These effects are easily seen by reference
to the results of Watanabe [31]. On the other hand, a poly-
mer that has high attraction forces between the chains will
expand less readily than a noninteracting polymer, there-
fore such an interacting polymer must be heated to a higher
temperature before the free volume becomes as large as re-
quired at the glass transition temperature. In the case of
poly(BPOEMA), the size of 1-Benzylpiperazine substituent
of poly(BPOEMA) is large, and raise the Tg by increasing
the interchain cohesive forces. On the other hand, the Tg of
polymer is related to the chain flexibility and this parame-
ter is to a large extent, a reflection of the rotational barrier
about the bond linking monomer unit. The cause of this
effect is not clear since chain flexibility not only depends
on the rotational barrier but also on the chain packing, side
chain stiffness, dipole interactions, etc. In DSC measure-
ments, Tg of poly(EMA) obtained under the same conditions
with the poly (BPOEMA) and poly(MPOEMA) was found
at 65 ◦C. The Tg of poly(BPOEMA) and poly(MPOEMA)
are compared to that of poly(EMA). The glass-transition
temperature of poly(BPOEMA) is considerably higher than
the other polymer [(poly(MPOEMA) and poly(EMA)]. Ap-
parently the bulky benzylpiperazine side group apparently
decreases the flexibility of the chain and the free volume
and increases the packing of chains, thereby increasing Tg .
According to Tg studies the order is poly(BPOEMA) >
poly(MPOEMA) > poly/EMA).
185
Figure 4. The TGA curves of polymers.
Decomposition Kinetics
The thermal stabilities of the polymers were investigated by
thermogravimetric analysis (TGA) in a nitrogen stream at a
heating rate of 10 ◦C min−1 . The TGA thermograms of poly-
mers are shown. From Figure 4, it is clear that two degrada-
tion stages for poly(BPOEMA) and three degradation stages
for poly(MPOEMA) are observed. Some numerical values
obtained from the TGA curves of the polymers are sum-
marized in Table 3. Poly(BPOEMA) and poly(MPOEMA)
were found to be more stable than poly(EMA). Accord-
ing to initial decomposition temperature studies at which
higher 50% weight loss are in the order poly(MPOEMA)
> poly(BPOEMA) > poly(EMA). The residue at 460 ◦C
are in the order poly(BPOEMA) > poly(MPOEMA) >
poly(EMA).
The thermal degradation of poly-n-alkyl methacrylates
typically produces the monomer as a result of depolymer-
ization. For the study on the kinetics of thermal degradation
of polymers we can select the isothermal thermogravime-
try (ITG) or the thermogravimetry (TG) at various heating
rates [32]. ITG is superior to obtain an accurate activa-
tion energy for thermal degradation, although it is time-
consuming. In the case of thermal degradation of polymers,
in which depolymerisation is competing with cyclization
or crosslinking due to the side groups, the TG at vari-
ous heating rates is much more convenient than ITG for
the investigation of thermal degradation kinetics. There-
fore, in the present work TG curves at various heating rates
were obtained and the activation energies (E d ) for ther-
mal degradation of polymers were calculated by Ozawa’s
plot, which is a widely used method. Degradations were
performed in the scanning mode, from 35 up to 500 ◦C,
under nitrogen flow (20 ml min−1 ), at various heating rates
(β : 2.0, 4.0, 7.0, 10.0, and 12.5 ◦C min−1 ). Samples of 5–
8 mg held in alumina open crucibles were used and their
weights were measured as a function of temperature and
stored in the list of data of the appropriate built-in program
of the processor. The TGA curves were immediately printed
at the end of each experiment and the weights of the sample
at various temperatures were then transferred to a PC.
186 C. Soykan et al.
Table 2. The apparent activation energies of polymers under thermal
degradation in N2

Activation energy E d (kJ/mol)

Conversion (%)

Sample 10 20 30 40 50 60 70 80

Poly(BPOEMA) 100.2 98.8 95.9 84.6 87.7 101.4 104.7 100.8

Poly(MPOEMA) 93.2 82.9 87.0 93.3 88.9 81.4 103.4 106.5

Table 3. Thermal decomposition data and activation energies of polymers

Sample Stages of Temperature Average activation

decomposition range (◦ C) energy (kJ/mol)

Poly(BPOEMA) Stage 1 200–350 96.1

Figure 5. The thermal degradation curves of poly(MPOEMA) at different
heating rates. (56)∗
Stage 2 350–420 102.8
(34)
Poly(MPOEMA) Stage 1 204–300 87.7
(28)
Stage 2 300–370 87.7
(35)
Stage 3 370–440 105.0
(33)
∗ Figures in paranthesis indicate weight loss (%) during the temperature
range stated.

that this result was similar to methacrylate polymers in the

literature [34, 35].

Figure 6. Ozawa’s plots of logarithm of heating rate (β) versus reciprocal
temperature (1/T) at different conversions for a poly(MPOEMA).
According to the method of Ozawa [19], the apparent
thermal decomposition activation energy, E d , can be deter-
mined from the TGA thermograms under various heating
rates, such as in Figure 5 [for poly(MPOEMA)], and the
following equation:


R d log β
Ed = − , (1)
b d(1/T )
where R is the gas constant; b, a constant (0.4567); and β,
the heating rate ( ◦ C/min). According to Equation (1), the
activation energy of degradation can be determined from the
slope of the linear relationship between log β and 1/T , as
shown in Figure 6 [for poly(MPOEMA)]; the apparent ther-
mal decomposition activation energies for poly(BPOEMA)
was calculated by the same methods. The E d values for
polymers are given in Table 2. E d calculated from the
Ozawa method is superior to other methods for complex
degradation, since it does not use the reaction order in
the calculation of the decomposition activation energy [33].
Therefore, E d calculated from the Ozawa method was su-
perior to the former methods for complex degradation. The
average activation energies corresponding to the different
stages have been calculated and listed Table 3. It is shown
Conclusion
The synthesis of new methacrylate esters having pendant
2-(4-benzyl piperazin-1-yl)-2-oksoethyl and 2-(-4-methyl-
piperidin-1-yl)-2-oksoethyl moieties have been reported.
The structure of both monomer and their polymers were
characterized by spectroscopic methods. The degradation ki-
netic of polymers were studied. The start of degradation is
due to the degradation of the starch main chain and the ester
of the polymer chain. And the latest of degradation is due to
the further degradation of the side group chain. The decom-
position activation energies were calculated employing the
Ozawa method.
Acknowledgement
The authors are very grateful to Prof. Dr. A. Zeki YILMAZ
who is president of Erciyes University, and Prof. Dr. Yunus
Akçamur who is Dean of Yozgat Faculty of Science and Arts
for supplying Thermal Analysis System to their department.
References
1. R. Arshady, J.M.S.-Rev. Macromol. Chem. Phys., C32(1), 101 (1992).
2. D. C. Sherrington and P. Hodge, Synthesis and Separations Using
Functional Polymers, Wiley, Chichester, 1988.
New Poly(Methacrylate)s Containing Benzylpiperazine and Methylpiperidine Moieties 187

3. P. D. G. Dean, W. S. Johnson and F. A. Middle, Affinity Chromatog- 18. A. Warshawsky, N. Kahana, V. Kampel, I. Rogachev, E. Meinhardt,
raphy, IRL Pres, Oxford, 1985. J. L. Cortina, R. M. Kautzmann and C. H. Sampaio, Macromol. Mater.
4. S. G. Allenmark, Enanthioselective Separations, Ellis Harwood, Eng., 286, 285 (2001).
Chichester, 1988. 19. T. Ozawa, Bull. Chem. Soc. Japan, 38, 1881 (1965).
5. R. B. Merrifield, Makromol. Chem. Suppl., 19, 31 (1988). 20. C. D. Doyle, J. Appl. Polym. Sci., 5, 285 (1961).
6. G. B. Fields and R. L. Noble, Int. J. Peptide Protein Res., 35(3), 161 21. C. D. Doyle, J. Appl. Polym. Sci., 6, 639 (1962).
(1990). 22. J. H. Flynn and L. A. Wall, Polym. Lett., 4, 323 (1966).
7. K. Mosbach (ed.), Methods in Enzymology, Vol. 11, Academic Pres, 23. L. Reich, Polym. Lett., 2, 621 (1964).
New York, 1985. 24. R. Simha and L. A. Wall, J. Phys. Chem., 56, 707 (1952).
8. J. Woodward, Immobilized Enzymes and Cells: A Practical Approach, 25. J. H. Flynn and L. A. Wall, J. Res. Nat. Bur. Stand., 70A, 487 (1966).
IRL Pres, Oxford, 1985. 26. S. Ichihara, H. Nakagawa and Y. Tsukazawa, Kobunshi Ronbunshu,
9. I. Chibata, T. Tosa and T. Sato, J. Mol. Catal., 37(1), 1 (1986). 51(7), 459 (1994).
10. W. T. Ford (ed.), Polymeric Reagents and Catalysts, American 27. H. Nishida, M. Yamashita and T. Endo, Polym. Degrad. Stab., 78, 129
Chemical Society, Sym. Ser. 308, Washington, DC, 1986, p. 1. (2002).
11. IUPAC Microsymposium on Reactive Polymers, Prague, Czechoslo- 28. J. Degutis, A. Undzenas and A. Urboravicius, U.S.S.R.-Patent-
vakia, 1987. 466227, 1975.
12. A. N. M. Kasim, D. Venkappayya and G. V. Prabhu, J. Indian. Chem. 29. R. Balaji, R. K. Subramanian, S. Nanjundan and A. V. Rami Reddy,
Soc., 76, 67 (1999). J. Appl. Polym. Sci., 78, 1412 (2000).
13. P. S. Desai and K. R. Desai, J. Indian. Chem. Soc., 70, 177 (1993). 30. E. L. McCafferty, Laboratory Preparation for Macromolecular
14. R. C. Paul, P. Kapila, A. S. Bedi and K. K. Vasisht, J. Indian. Chem. Chemistry, McGraw-Hill, New York, 1970, p. 22.
Soc., 53, 768 (1976). 31. S. Watanabe and M. Kato, J. Polym. Sci. Polym. Chem. Edn., 22, 2801
15. V. H. Shah, H. H. Patel and A. R. Parikh, J. Indian. Chem. Soc., 59, (1984).
678 (1982). 32. W. W. Wendlandt, Thermal Analysis, 58(5), R1–R6, 57 (1986).
16. J. L. Cortina, A. Warshawsky, N. Kahana, V. Kampel, C. H. Sampaio 33. N. Regnier and C. Guibe, Polym. Degrad. Stab., 55(2), 165 (1997).
and R. M. Kautzmann, Reactive and Functional Polymers, 54, 25 34. B. C. Ho, Y. D. Lee and W. K. Chin, J. Polym. Sci: Part A, Polym.
(2003). Chem., 30(11), 2389 (1992).
17. A. Warshawsky, N. Kahana, V. Kampel, I. Rogachev, E. Meinhardt, 35. S. Y. Lin, C. M. Liao and G. H. Hsiue, Polymer, 36(16), 3239 (1995).
J. L. Cortina, R. M. Kautzmann and C. H. Sampaio, Macromol. Mater.
Eng., 283, 103 (2000).