International Journal of Organic Chemistry, 2011, 1, 57-69
doi:10.4236/10200011 Published Online June 2011 (
Copyright © 2011 SciRes. IJOC
Synthesis, Kinetics and Mechanism of Terpolymerization of
S tyrene, Vinyl Acetate with Acrylonitrile Initiated by
P-Nitr obenzyl Triphenyl Phosphonium Ylide
Kiran Prajapati, Anuradha Varshney*
Chemistry Department, D. G. College, Kanpur, India
Received April 1, 2011; revised May 17, 2011; accepted May 28, 2011
Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one
electron-accepting monomer, i.e. acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in dioxane
as diluent at 65˚C for 150 min has been studied. The kinetic expression is
0.81.2 1.41.2
. The
terpolymer composition was determined by the Kelen-Tüdos method. The values of reactivity ratios using
r1 (Sty + VA) = 0.1 and r2 (AN) = 0.005. The overall activation energy is 46 kJ mol L–1. The formation of
terpolymer is confirmed by the FTIR spectra showing bands at 3030 cm–1, 1598 cm–1, and 2362 cm–1, con-
firming the presence of phenyl, acetoxy and nitrile group respectively. The terpolymer has been character-
ized by 1H-Nuclear Magnetic Resonance, 13C-Nuclear Magnetic Resonance. The Differential Scanning
Calorimetric curve shows the Tg of the polymer as 149.5˚C. A scanning electron microscope confirms the
polymer to be phosphorus free. Electron.Spin.Resonance spectra confirms phenyl radical responsible for
Keywords: P-Nitrobenzyltriphenyl Phosphonium Ylide (P-NBTPY), Terpolymer, Kinetics, Mechanism
1. Introduction
The interest in macromolecular architecture has in-
creased dramatically in recent years. Terpolymerization,
i.e. three component polymers has continued to attract
the attention of both academics and industrialists due to
their unique properties and potential application. One of
the main advantages of this technique is that it allows
information to be obtained on a class of monomers which
is otherwise not available. Although voluminous litera-
ture is available for homo, and copolymerization very
little kinetic and synthetic information is available for
terpolymerization. This is due to wide variation in
monomer reactivity with radicals and difficulty of si-
multaneous polymerization of three monomers together.
A search of literature reveals that few terpolymer sys-
tems have been reported i.e. , (styrene-acrylonitrile-
Chromium acrylate)) and (styrene-Methyl meth acry-
late-acrylonitrile) initiated by styrene arsenic sulfide
complex [1-2] and (citronellol-styrene-methyl methacry-
late) initiated by benzylperoxide[3], (styrene-acryloni-
trile-copper acrylate) initiated by p-Acetyl benzylidene
triphenyl arsoniumylide[4]. Recently, Zhang [5] prepared
gradient polymer by complex radical terpolymerization
of styrene, maleic anhydride and N-vinyl pyrrolidone via
gamma ray irradiation and Lodge[6] synthesized Three
poly(ethylene-alt-propylene)-b-poly (ethyleneoxide)-b-
poly(N-opropylacrylamide) (PEP-PEO-PNIPAm, “PON”)
triblock terpolymers using a combination of anionic and
reversible addition-fragmentation chain transfer polym-
erization, and their micellization and micellar aggrega-
tion properties in dilute aqueous solution by dynamic
light scattering (DLS) and cryo-TEM. An ylide is sub-
stance in which a carbanion is attached directly to a het-
eroatom carrying high degree of positive charge repre-
sented by the general formula I :
> C – X <
Wittig reaction, a novel method for conversion of car-
bonyl group into olefinic functions has altered the role of
ylide, moving them from the realm of chemical curiosi-
ties into the arsenal of important synthetic tools.
The special characteristic of ylides that make them
worthy of study in their own right is the unique stabiliza-
tion afforded by the carbanions by the presence of the
adjacent onium atom groups. Ylides have wide applica-
tion [7] as reaction intermediate, synthetic and organic
chemistry, and polymerization catalyst. Ylides with het-
eroatom, bismuth, nitrogen, sulphur, arsenic, antimony
are also reported as initiators [8], retarders [9], degrada-
tive transfer agents [10] in the polymerization vinyl
monomers. The application of phosphorus ylide in do-
main of polymer science is scarce [11-13].
Phosphorous ylide are reactive and unless special
structural features, have been incorporated and are usu-
ally not capable of isolation. The sufficient stability of
the phosphorus ylide to be capable of isolation has been
attributed to the structural and electronic factors which
contribute to stabilization of the ylidic carbonion. This
stabilization has been thought to results from delocaliza-
tion of the non-bonded electrons of the carbanion. In a
given ylide, X-CR2, stabilization for the carbanion could
be afforded by both the heteroatom portion (X) and the
two carbanion substituents (R). The ability of the groups
R to delocalize the carbanionic electrons does affect the
stability of the ylide. However, it is equally apparent that
this stabilization is not sufficient in itself to account for
the unique stability of phosphorus ylides. The phospho-
rus atom itself must play an important role in the stabili-
zation of the carbanion. The stabilization has been attrib-
uted to the use of the vacant 3d-orbitals of the phospho-
rus atom, the carbanion taking advantage of the ability of
the phosphorus atom to expand its Outer shell to ac-
commodate more than eight electrons. The pΠ-d Π
bonding in phosphorus ylide is controversial regarding
structure and bonding [14].
Because of lack of data for the radical polymerization
of Sty, AN, VA, it is very interesting to investigate its
terpolymerization in the sequence of our continuing work
[15]. Therefore, attempts have been made to synthesis
the terpolymer and study the kinetics and characteriza-
tion of the terpolymer initiated by p-nitrobenzyltri-
phenyl phosphonium ylide.
2. Experimental
2.1 Materials
Styrene (Sty), vinyl acetate (VA) and acrylonitrile (AN)
(Merck) were washed with 4% sodium hydroxide and
distilled water [16]. The dried monomers were then dis-
tilled under reduced pressure. Triphenyl phospine
(Merck) was used as received. P-nitrobenzyl triphenyl
phosphnium ylide (p-NBTPY) was prepared by the
method reported by McDonald and Campbell as reported
in our earlier issue [11].
Briefly the synthesis of ylide is as follows: (Scheme 1)
2.2 Characterization of P-Nitrobenzyltriphenyl
Phosphonium Bromide
1) M. P. –275˚C
2) Elemental analysis -
Analysis calculated for C25H21 NO2Br :
C, 63.0; H, 4.0; N, 2.93
Found: C, 62.6; H, 4.2; N, 3.14
3) FTIR (KBr) (Figure 1)
Aromatic C – H stretching 3050 cm–1
Scheme 1
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Aromatic C = C stretching 1483 cm–1
A symmetric (ArNO2) 1517 cm–1
Symmetric (ArNO2) 1344 cm–1
ArNO2, C – N stretching 850 cm–1
C – Br stretching 540 cm–1
4) 1H-NMR (Figure 2)
(2 H – P+ – CH2) Singlet at 3.4 δ ppm
Multiplet of 19 H, Aromatic 7.68 - 7.85 δ ppm.
2.3. Terpolymerization
The terpolymerization runs were carried out in a dila-
tometer (dia = 2 mm, length =10 cm, capacity = 3 ml).
The polymerization solution was prepared by taking
requistic quantities of all the three monomers, along-
with. p-nitrobenzyl triphenyl phosphnium ylide (p-
NBTPY) in dioxane as an inert solvent. The polymeri-
zation was carried out for 150 min at 65˚C ± 1˚C under
nitrogen blanket. The terpolymer was precipitated with
methanol. The terpolymer formed was refluxed with
solvents, benzene, tetrahyrofuran and dimethylforma-
mide to remove homo and copolymers. The weight loss
in each refluxing was negligible. The rate of polymeri-
zation (Rp) was calculated from the slope of the conver-
sion versus time plots [17].
Tr ans
ittance [
0.550.60 0.65
Wavenumber cm-1
3500 2000
3000 1500 1000 500
Figure 1. FTIR spectrum of p-nitrobenzyl triphenyl phos-
phonium bromide.
Figure 2. 1H-NMR spectrum of p-nitrobenzyl triphenyl
phosphonium bromide.
2.4. Characterization
Fourier Transform Infrared Spectroscopy: FTIR spectra
were recorded with Perkin-Elmer 599B in Dichloro-
methane. NMR Spectroscopy: 1H-NMR and 13C-NMR
spectra were recorded with a Varian 100HA Jeol LA 400
spectrometer by using CDCl3 as solvent and tetramethyl
silane as internal reference. DSC Analysis: were carried
out by using Perkin-Elmer; Pyris Diamond differential
scanning calorimetry; sample weight 2.43 mg at heating
rate 10˚C and temperature range 0˚C - 500˚C. SEM
Analysis was conducted in Jeol JSM 840 A scanning
electron microscope. Sample was mounted on a brass
stub using an adhesive and were gold coated. GPC: The
GPC studies were made with a water 200 model using
THF as a solvent at 25˚C. E.S.R Analysis was conducted
in Brucker EMX E.S.R spectro-photometer, Model
3. Result and Discussion
P-nitrobenzyl triphenyl phosphonium ylide initiated
radical terpolymerization of styrene, vinylacetate and
acrylonitrile. All the reactions are associated with induc-
tion period of about 2 - 16 min. The conversion was re-
stricted upto 16.3%. The kinetics of terpolymerization
was studied by varying. P-nitrobenzyl triphenyl phosph-
nium ylide (Figure 3) from 16.8 × 10–6 mol L–1 to 51.3 ×
10–6 mol L–1, keeping [Sty] [VA] and [AN] constant at
1.44 mol L–1, 1.44 mol L–1, 2.01 mol L–1 respectively.
The effect of p-nitrobenzyl triphenyl phosphnium ylide
on rate of polymerization (Rp) is shown in Table 1. The
Rp increases with increasing concentration of.
p-nitrobenzyl triphenyl phosphnium ylide as expected for
free radical terpolymerization. The order of reaction with
respect to p-nitrobenzyl triphenyl phosphnium ylide is
calculated from the slope of the plot of (Figure 4) log Rp
versus log [p-NBTPY] is 0.8.
Wavenumber cm–1 The effect of monomer on the rate of polymerization is
summarized in Table 2. The effect of [Sty] on Rp has
been studied by varying [Sty] from 0.288 mol L–1 to 2.59
mol L–1, keeping –1 [VA], [AN] and [p-NBTPY] constant
at 1.44 mol L–1, 2.01 mol L–1 and 33.6 × 10–1 mol L–1
respectively. A plot of log Rp and log [Sty] (Figure 5) is
linear, the slope of which gives the relationship. Equa-
tion (1)
The effect of [VA] on Rp has been studied by varying
[VA] from 0.72 mol L–1 to 2.88 mol L–1, keeping [Sty],
[AN] and [p-NBTPY] constant at 1.44 mol L–1, 2.01 mol
L–1 and 33.6 × 10–6 mol L–1 respectively. A plot of between
log Rp and log [VA] (Figure 6) is linear, the slope of
which gives the relationship: Equation (2)
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Time in min Time in min
Time in min
Figure 3. Time conversion profile in the ternary polymerization of Sty, VA, AN with [p-NBTPY] as radical initiator at 65˚C
in dioxane.
Table 1. Effect of [p-NBTPY] on the rate of terpolymerization.
Sample No. p-NBTPY × 10–6 mol. L–1 Percentage conversion Rp × 106 mol. L–1s–1
1. 16.8 6.4 4.075
2. 25.2 8.2 4.89
3. 33.6 10.6 5.705
4. 42.0 12.4 7.335
5. 51.3 15.2 8.965
[Sty] = 1.44 mol L–1, [VA] = 1.44 mol, L–1 [AN] = 2.01 mol. L–1 Time = 150 min, Temperature = 65˚C ± 1˚C.
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Table 2. Effect of [monomers] on the rate of terpolymerization of (styrene-co-vinyl acetate-co-acrylonitrile) initiated by
Sample No. Monomers Percentage conversion Rp × 106
mol. L–1s–1
6 [Sty]* 0.28 7.02 3.11
7 0.86 8.35 4.31
8 2.01 13.9 9.1
9 2.59 15.6 11.07
10 [VA]** 0.72 9.1 4.17
11 2.16 11.4 7.48
12 2.88 14.3 11.60
13 [AN]*** 1.00 5.6 2.58
14 3.01 12.1 8.83
15 4.02 15.7 11.50
*[VA] = 1.44 mol L–1, [AN] = 2.01 mol. L–1, (p-NBTPY) = 33.6 × 10-6 mol L–1 **[Sty] = 1.44mol L–1, [AN] = 2.01 mol L–1, (p-NBTPY) = 33.6
× 10–6 mol L–1 ***[Sty] 1.44 mol L–1, [VA] =1.44 mol L–1, (p-NBTPY) = 33.6 × 10–6, mol L–1 Time = 150 min, Temperature = 65˚C ± 1˚C.
log Rp + 6
log Rp + 6
Figure 4. Plot for log Rp versus log [p-NBTPY].
Figure 6. Plot of log Rp versus log [VA].
log Rp + 6
log Rp + 6
Figure 5. Plot of log Rp versus log [Sty].
Figure 7. Plot of log Rp versus log [AN].
exponents can be explained on the basis of primary radical
termination [18] and degradative chain transfer [19].
The effect of [AN] on Rp has been studied by varying
[AN] from 1.00 mol L–1 to 4.02 mol L–1, keeping [Sty],
[AN] and [p-NBTPY] constant at 1.44 mol L–1, 1.44 mol
L–1 and 33.6 × 10–6 mol L–1 respectively. A plot of be-
tween log Rp and log [AN] (Figure 7) is linear, the slope
of which gives the relationship : Equation (3)
Primary radical termination was explained by the ex-
pression given by Deb and Meyerhoff. This expression
has been frequently used for terpolymerization [20].
Equation (4)
 
loglog 0.864
pkdp prt
 p
The deviation in the values of initiator, Sty, VA and AN
where fk represents the fraction of free radical to initiat-
ing chain growth, kd is the initiator decomposition rate
constant, kp is the propagation rate constant, and kprt is
the primary radical termination constant, [M] is the
monomer concentration.
The plot (Figure 8) of the left-hand side of the afore-
mentioned equation versus Rp/[M]2 gave a negative
slope, indicating significant primary radical termination.
The equation by Ghosh and Mitra [21] was used to
examine degradative chain transfer reactions as follows:
Equation (5)
 
loglog 0.434M
where CI is the initiator transfer constant, krtI is the rate
constant of degradative chain transfer to initiator and kiI
is the initiator rate constant.
A plot (Figure 9) of the left hand side of the preceding
equation versus [I]/[M] gave a negative slope. The de-
viation in the exponent value of initiator and monomers
in the present system appears due to both primary radical
termination and degradative chain transfer.
Effect of temperature:
The polymerization runs were carried out at 55˚C, in-
creases with increase in temperature. The energy of acti-
Figure 8. Plot of Rp2/[I] [M]2 versus Rp/[M]2.
Figure 9. Plot of Rp2/[I] [M]2 versus [I]/[M].
vation was calculated from the Arrhenius plot (Figure 10)
as 46 kJ/mol
Characterization of the terpolymer:
FTIR: The FTIR (Figure 11) spectra[22] of the ter-
polymer exhibit characteristic absorption band at 3430
cm–1, 1598 cm–1, 2362 cm–1 of phenyl group, acetoxy
group and nitrile group respectively. This confirms the
incorporation of all the three monomers in the terpoly-
1H-NMR: The 1H-NMR spectra[22] shows (Figure
12) a multiplet at 7.6 to 7.9 δ ppm due to phenyl protons
of styrene and the peak at 2.1 δ ppm to the acetoxy pro-
tons of vinyl acetate characteristic chemical shift values
of the methane and methylene protons of polymer back-
bone chain were at 1.0 - 3.8 δ ppm.
13C-NMR: The 13C-NMR spectra (Figure 13) of the
terpolymer showed a peak at 175 due to the carbonyl
carbon of vinyl acetate 137 δ ppm at aromatic carbon
resonance of the styrene and at 128 ppm due to nitrile
carbon of acrylonitrile also confirms incorporation of all
the three monomers in the polymer.
GPC: The GPC Parameters are presented in Table 3.
It appears from the molecular data of the terpolymer that
with increase in the initiator concentration the (V
viscosity average molecular weight decreases with the
increase in initiator concentration because of increased
number of radicals in the medium.
DSC Analysis:
The DSC curve (Figure 14) indicates that the glass
transition temperature (Tg) of (Sty-co-VA-co-AN) is
149.5˚C. The transition of melting range originate from
377˚C and the terpolymer is decomposed completely at
404˚C. The Tg evaluated from the experimental data is in
excellent agreement with the calculated one.
The calculated Tg from the Fox equation [23] Equation
(6) below is 154˚C
gg g
Figure 10. Arrhenius plot of log Rp versus 1/T × 103.
log Rp + 6
log Rp2
[I] [M]2
log Rp2
[I] [M]2
1/T × 103
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Figure 11. FTIR spectral analysis of terpolymer of sample No. 3.
Figure 12. 1H-NMR spectral analysis of terpolymer sample No. 3
Table 3. G.P.C Parameters of terpolymer (p-NBTPY variation).
Average Z average Viscosity
[int] w
1. 49391 321579 838082 778997 0.00058 6.5 16.9 2.4 2.6
3. 18613 43925 396191 363988 0.00046 7.73 21.28 2.52 2.75
5. 13735 38404 74420 73964 0.00028 2.79 5.41 1.92 1.93
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Figure 13. 13C-NMR spectral analysis of terpolymer sample No. 3.
Wavenumber (˚C)
Figure 14. DSC curve of terpolymer sample No. 3.
where the composition for [Sty] W1 = 25, Tg = [100˚C]
[24], [AN] W2 = 50, Tg = [97˚C] [23], [VA] W3 = 25, Tg
= [32˚C] [26]. Nevertheless, the observation of a single
Tg and a Tg close to that predicated by equation indicates
complete mixing during free radical polymerization.
SEM: The terpolymer obtained was phosphorus free.
The absence of phosphorus is confirmed by a qualitative
test using concentrate nitric acid and ammonium molyb-
date where yellow precipitate was not obtained. SEM
report (Figure 15) also indicates the absence of phos-
phorus in the polymer.
Reactivit y R at i o:
The relative area of peaks at 7.6 - 7.9 δ ppm (due to
phenyl protons) of [Sty] and a peak at 2.1δ ppm (due to
Figure 15. SEM report of terpolymer sample No. 3.
acetoxy protons) of vinyl acetate, acrylonitrile content
from the nitrogen percentage are used to calculate the
reactivity ratios. The composition of terpolymer are
shown in Table 4.
The Kelen-Tüdos [27] approach is used for evaluation
of reactivity ratios, monomer according to taking Sty and
VA as r1 and AN as r2. The equations Equation (7) are:
the transformed variables G and H are given by
 
121 2
M/M dM/dM1
d MdM
 
d MdM
The parameter is calculated by the square root of the
product of the lowest and highest values of H for the
copolymerization series. The graphical evaluation (Fig-
ure 16) for Sty and VA yield values of r1 = 0.1 and AN
yields value of r2 = 0.005. The product of r1 r2 is nearly
zero, which is the sign of alternating terpolymerization.
P-NBTPY ylide is considered to be the resonance hy-
brid of the following structure. (see Machanism)
As reported in the literature [11], the initiator under-
goes bond fission between the heteroatom and phenyl
group on irradiation by a high pressure mercury lamp
and the phenyl radicals produced participate in the initia-
tion of the polymerization. From structural similarity, it
seems that p-NBTPY also undergoes similar fission and
phenyl radical participates in the initiation. This was
confirmed by the ESR results (Figure 17) that the ylide
dissociates, yielding a phenyl free radical. It also con-
firms the free radical mode of polymerization giving the
value of gyromagnetic ratio “g” as 2.11. It matches well
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Table4. Composition of terpolymer.
Monomer composition
Sample No. Monomer feed
Polymer feed
(f) % Conversion Mole fraction
of [Sty]*
Mole fraction of
Mole fraction of
03 1.43 1.4 10.6 1.44 1.44 2.01
06 2.00 1.9 7.02 0.28 1.44 2.01
09 0.85 0.98 15.6 2.59 1.44 2.01
10 0.71 0.37 9.1 1.44 0.72 2.01
12 2.88 2.31 14.3 1.44 2.88 2.01
13 2.14 1.8 5.6 1.44 1.44 1.00
15 1.074 0.96 15.7 1.44 1.44 4.02
*Calculated from peaks due to phenyl proton. **Calculated from peaks due to acetoxy proton; ***Calculated from nitrogen percent via elemental analy-
sis; [p-NBTPY] = 33.6 × 10–6 mol L–1, temperature = 65˚C ± 1˚C, Time = 150 min.
Figure 17. ESR spectrum of terpolymer sampl e No. 3.
Figure 16. Kelen-Tüdos plot of terpolymer for determina-
tion of reactivity ratio.
capable of initiating the polymerization of (Sty-co-AN-
co-VA) in dioxane solution giving in alternating ter-
polymer without using Lewis acid. The formation of
terpolymer is confirmed by the FTIR spectra showing
bands at 3030 cm–1, 1598 cm–1, and 2362 cm–1, confirm-
ing the presence of phenyl, acetoxy and nitrile group
respectively. SEM confirms the polymer to be phospho-
rus free. E.S.R. spectra confirms phenyl radical respon-
sible for initiation.The DSC studies evidenced the glass
transition temperature of terpolymers as 149.5˚C.
with the value given for free radical polymerization. The
spectra shows[28] six hyperfine lines and hyperfine con-
-stant as 3.74 (G) . The free radical mode of polymeriza-
tion was also confirmed by the inhibitory effect of hy-
droquinone on the rate of polymerization.
4. Conclusions
p-nitrobenzyltriphenyl phosphonium ylide (p-NBTPY)is
5. Acknowledgements
The authors are grateful to the Dr. Meeta Jamal, Princi-
pal Dayanand Girls College, Kanpur, India for providing
necessary facilities, Dr. A. Varshney is thankful to
U.G.C. New Delhi for sanctioning the project entitled
“Polymerization of vinyl monomers using ylide and
metal ylide complexes as new radical initiators
(F.12-5/2004 (SR)).
One of the author (K.P.) is thankful to the Under Sec-
retary, Uttar Pradesh Shasan, India for sanctioning the
study leave to conduct this research.
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Analysis Report
General Conditions
Result File : Terpolymer
File Version : 1
Background Method : Auto
Decon Method : Gaussian
Decon ChiSquared : 11.18
Analysis Date : 19-March-2005
Microscope : SEM
Comments :
Quant. Method : XPP/ASAP
Acquire Time : 50 sec
Nationalization Factor : 100.00
Kv : 15.0
Beam Current : 137.9 picoAmps
Working Distance : 25.0 mm
Tilt Angle : 0.0 Degrees
Take Off Angle : 35.0 Degrees
Solid Angle *Beam Current : 1.2
Element Line Weight% K-Ratio Decon Region Cnts/s Atomic%
P Ka 0.00 0.0000 0.000 - 0 0.00 0.00
Cu Ka 4.03 0.0528 7.660 - 8.430 25.99 10.77
Pd La 1.30 0.0090 2.640 - 3.040 16.47 2.08
Au La 91.54 0.8896 9.220 - 10.13 41.58 79.00
Zn Ka 3.14 0.0429 8.230 - 9.030 15.51 8.15
Total 100.01