J Polym Res (2008) 15:187–193
DOI 10.1007/s10965-007-9158-y
Studies on the radical polymerization of N-vinyl
2-pyrrolidone initiated by diphenyl ditelluride
Anjali Tripathi & A. K. Srivastava
Received: 11 April 2007 / Accepted: 25 September 2007 / Published online: 4 December 2007
# Springer Science + Business Media B.V. 2007
Abstract N-vinyl pyrrolidone (NVP) was polymerized in
dioxan at 60±0.1°C for 1 h using diphenyl ditelluride as
radical initiator. The system follows ideal kinetics i.e. Rp α
[DPDT]0.5[NVP]. The activation energy and dissociation
constant is computed as 46 kJ mol−1 and 1.1×10−11 s−1,
respectively. The polymer was characterized with the help
of FTIR, 1H-NMR, 13C-NMR, ESR spectroscopy. The FT-
IR spectrum showed bands at 1660–1680 cm−1 due to
combination of >C=O and C–N stretching. The gyromag-
netic constant ‘g’ has been computed as 2.2203. The main
product of this reaction were poly(N-vinylpyrrolidone)s
with phenyl tellanyl ends. The presence of tellurium in
polymer is confirmed by ICP analysis. The DSC shows the
Tg of poly(N-vinylpyrrolidone) is 168°C due to rigid
pyrrolidane group. The TGA showed that polymer was
stable up to 380°C.The GPC studies showed that the weight
average molecular weight decreases with increase of
[DPDT].
Keywords N-vinylpyrrolidone . Diphenyl ditelluride .
Kinetics and mechanism
Introduction
Polymeric materials have been extensively used in medi-
cine and surgery. Numbers of polymers have been prepared
A. Tripathi : A. K. Srivastava (*)
Department of Chemistry, H.B. Technological Institute,
Kanpur 208 002, India
e-mail: akspolym@rediffmail.com
and characterized for this use as biomaterials. Over the past
50 years, N-vinyl-2-pyrrolidone polymers (NVP) have
been widely used, especially in pharmaceutical, cosmetic,
textile and food industry as well as for numbers technical
applications. From the pharmaceutical point of view
soluble grades of amorphous poly(vinylpyrrolidone)s
possess a number of very useful properties viz. good
biocompatibility solubility in all conventional solvent,
adhesive and binding power, film formation, ability to
form complexes, availability in different molecular
weights, thickening properties [1]. Due to its high Tg,
NVP polymers are attractive in polymer science as a result
of the strong economic incentives that arises from this
potential applications [2].
Few cationic [3] and radical initiators [4] are available for
the polymerization of NVP. The role of organotellurium
compounds like diphenyl ditelluride(DPDT) in polymer
chemistry is still infancy. Takagi et al. [5] reported the
polymerization of styrene initiated by ditelluride at 125°C.
The authors reported that it initiated polymerization at 90°C,
with almost negligible percent conversion but at 125°C it was
up to 87%.The concentration of DPDT was high (8.7 mmol s)
in all cases. The author used combination of AIBN or BPO as
radical initiator and DPDT as a reagent to control molecular
weight for radical polymerization of styrene. Yoshida et al. [6]
carried out organotellurium mediated living radical homo-
polymerization of styrene, butyl acrylate, methyl methacry-
late by in situ generated initiators from AIBN & ditellurides.
We have also reported homopolymerization of MMA [7] and
copolymerization of MMA with NVP [8] using DPDT in
dioxin as radical initiator at 60°C for 2 h and 1 h,
respectively. The present article highlights the kinetics and
mechanism of homopolymerization of NVP using DPDT as
a radical initiator at 60°C for 1 h.
188 A. Tripathi, A. Srivastava

Experimental section Table 1 Effect of [DPDT],[NVP] on rate of polymerization (Rp)

S. [DPDT]× [NVP] Percent Rp × Mw

Materials NVP (Merck) was vacuum distilled prior to No. 10−3 mol l−1 mol l−1 conversion 106 mol
polymerization .The solvents used were purified as per l−1 s−1
standard procedures [9]. DPDT was synthesize in our
1 2.45 1.56 5.4 1.14 97,226
laboratory according to published literature [10].
2 7.35 1.56 6.8 1.41 89,848
3 12.25 1.56 7.2 2.19 79,171
4 17.15 1.56 8.5 2.63 62,456
5 22.05 1.56 12.4 2.88 47,179
Polymerization procedure 6 12.25 0.31 4.8 0.28 –
7 12.25 0.94 6.7 0.89 –
Kinetic procedure 8 12.25 2.19 9.0 3.09 –
9 12.25 2.82 10.3 4.17 –
The runs were performed in dilatometer for 1 h at 60±
0.1°C under nitrogen atmosphere. The polymer(s), pre-
cipitated with diethyl ether, were dried to constant weight. 3, 4, 5 and 6. The reaction proceeds with an induction
The polymer(s), were reprecipitated 3 times. The rate of period of about 3 min.
polymerization (Rp) was calculated from the slopes of the 1. Effect of [DPDT] on rate of polymerization (Rp)
linear zone percent conversion vs. the time plots. The effect of [DPDT] on polymerization (Rp) has been
studied from 2.45×10−3 to 22.05×10−3 mol l−1 (Table 1)
Molecular weights (Fig. 1). The Rp increases with [DPDT] and the exponent
value has been calculated as 0.5 from the linear plot of log
The viscosities of PNVP were determined using an Rp vs. log DPDT (Fig. 2). The GPC data showed that the
ubbelohde viscometer at 30°C using methanol as solvent. weight average molecular weight decreases (96200–34340)
The intrinsic viscosity [η] in dl/g was then obtained by with increase of [DPDT](2.45×10−3–22.05×10−3) and PDI
extrapolation of a plot ηsp/C vs. C to infinite dilution. The was found broader (Table 2).
weight average molecular weights were then calculated
using Eq. 1 given by Levy & Frank [11].

½h
¼ 23  105 M w
0:65
ð1Þ

Polymer characterization

The Fourier-Transform Infrared (FTIR) spectrum was

recorded with Perkin-Elmer 599 B, with KBr Pellets. 1H-
NMR spectrum was recorded with a Varian 100 HA Jeol
LA 400 spectrophotometer using CDCl3 as solvent and
tetramethyl silane as internal reference. The ICP-MS was
carried out by Perkin-Elmer Optima 3000 ICP spectrome-
ter. The DSC runs were carried out using VA OB Dupont
2100 analyzer, sample weight 2.400 mg as a heating rate of
10°C/ min. The TGA were carried out using VS 1A Dupont
2100 analyzer at heating rate of 10°C/min from room
temperature to 600°C. The GPC studies were made with a
water 200 model using THF as a solvent at 25°C.

Results and discussion

The kinetics of reaction was studied by varying the [DPDT)
and [N-VP] at 60±01°C for 1 h. under the blanket of
nitrogen gas. The results of kinetics investigations of the
polymerization of NVP are shown in Table 1 and Figs. 1, 2,
Fig. 1 Percentage conversion versus time plots for the homopolyme-
rization of N-VP. [DPDT]=2.45×10−3–22.05×10−3 mol l−1(filled
circle 2.45×10−3 mol l−1, bullet 7.35×10−3 mol l−1, filled triangle
12.25×10−3 mol l−1, filled square 17.15×10 −3 mol l−1, open square
22.05×10−3 mol l−1). [NVP]=1.56 mol l−1
Studies on the radical polymerization of N-vinyl 2-pyrrolidone initiated by diphenyl ditelluride 189

Fig. 2 Plot for log Rp versus log [DPDT]; [NVP]=1.56 mol l−1 Fig. 4 A plot of versus [DPDT]

Determination of Dissociation Constant (kd) and initiator concentration. The rate of polymerization
It is difficult to measure concentration of phenyl telluro increases with temperature and overall activation energy
radical as well as DPDT , hence the decomposition rate . (ΔE), calculated from the corresponding slope of the
However decomposition constant (kd) has been calculated Arrhenius plot of log Rp vs. 1/T is 46 kJ/mol. (Fig. 7).
using Eq. 2
 
Rp ¼ kpðkd=ktÞ1=2 f 1=2 ½I
1=2 ½M
ð2Þ
  Spectral analysis
Where k  p=k t 1=2 has been deduced graphically from the
plot of 1 M w vs. Rp/[M]2 (Fig. 3) .The kd has been (a) Fourier Transform Infrared Spectroscopy:
determined as 1.1×10−11 s−1 from the slope of the plot of The FTIR spectrum showed the characteristic absorption
the Rp2/[M]2 vs. [DPDT] (Fig. 4) (Assuming initiator band of NVP at 1660–1680 cm−1 and is attributed to the
efficiency [12] (f)=1)
2. Effect of [NVP] on rate of polymerization (Rp): The
effect of [NVP] on the Rp was studied by varying the
[NVP] from 0.31 to 2.82 mol l−1 (Table 1 and Fig. 5).
The rate of polymerization (Rp) increases with [NVP],
the monomer exponent value, calculated from the slope
of a linear plot of log Rp vs. log [NVP] is unity (Fig. 6).
3. Effect of Temperature: The rate of polymerization was
measured at 5 different temperatures at a fixed monomer

Fig. 5 Percentage conversion versus time plots for homopolymeriza-

tion of NVP [DPDT]= 12.25 × 10−3 mol l−1[NVP][NVP] = 0.31–
2.82 mol l−1 (filled circle) 0.31 mol l−1 (bullet) 0.94 mol l−1 (filled
triangle) 1.56 mol l−1 (filled square) 2.19 mol l−1 (open square)
Fig. 3 A plot of 1/Mw versus Rp/[M]2 2.82 mol l−1
190 A. Tripathi, A. Srivastava

Fig. 7 Arrhenius plot of Rp versus polymerization temperature;

[NVP]=1.56 mol l−1, [DPDT]=12.25×10−3 mol l−1

Fig. 6 Plot of log Rp versus log [NVP]; [DPDT]=12.25×10−3 mol l−1

(d) 13C-Nuclear Magnetic Resonance Spectroscopy :

combination of >C=O and C–N Str [13]. Owing to this
combination mode, this band occurred broadly at a lower
wavenumber than the pure carbonyl band expected at
1750–1700 cm−1. FTIR spectrum of the NVP [14]
(Fig. 8) shows the following bands :
1. Band of C–N group at 1,290 cm−1
2. Band of >C=O at 1,700 cm−1
(b) Proton Magnetic Resonance Spectroscopy: The PMR
spectrum (Fig. 9) of the PNVP shows following peaks:
(1)= 1.5 δ ppm, (2) = 3.8 δ ppm, (4) = 2.3 δ ppm, (5) = 1.9 δ ppm,
(6) = 3.2 δ ppm (7) 7-8 ppm.
(c) Inductively Coupled Plasma-Mass Spectrocopy
The PNVP contains tellurium in it as suggested by the
ICP-MS analysis (Table 3). This is also confirmed by
qualitatively using concentration HNO3 and hydrazine
hydrate (NH2. NH2. H2O) ,when black precipitate is
obtained.
Table 2 GPC details
The 13C-NMR (Fig. 10) shows both the chain methylene
and methine carbon resonances and resolvable stereo
chemical splitting. It shows five groups of methylene
carbon peak centered at 36.2, 35.5, 34.6, 33.8 and
33.1 ppm and three major methine carbon peak at 46.7,
46.1 and 45.6 ppm, respectively. These peak positions are
in good agreement with those found by Cheng et al. [15]
and Dubroveen and Panov [16]. The carbonyl carbon peaks
at 178.5, 178.3 and 178.0 ppm which are assigned to the
triads rr, mr and mm, respectively.
The formation of meso diads in polymer chain increases
with increase in polymerization temperature, but it does not
follow always. It was shown that in vinyl carbazole
formation of racemic diads increase with increasing the
polymerization temperature [17]. The activation enthalpy
difference for meso and racemic diad formation is deter-
mined mainly by a difference in stabilization energy due to
electronic interaction in the transition state rather than a
difference in repulsion energy due to steric hinderance.
(e) Electron Spin Resonance Spectroscopy:
In order to ensure radical nature of reaction, we have
also run ESR spectrum (Fig. 11), which showed presence of
a singlet, which is attributed to phenyl tellurium radical

Ph  Te . The gyromagnetic constant ‘g’ has been
computed as 2.2203 (although this value is higher to the
radicals, where ‘g’=0.8036 [18]), which confirms free
radical mode of polymerization.

S. [DPDT]×10−3 mol Mw Polydispersity index

No. l−1 (PDI)
Thermal analysis
1 2.45 96,200 2.00
2 7.35 62,700 1.95 The Tg of the polymer measured by DSC scan, is 168°C
3 12.25 54,150 1.90
(Fig. 12). Literature survey reveals [19] that the Tg of NVP
4 17.15 46,686 1.86
ranges from 54° to 175°C. This is attributed to the large
5 22.05 34,340 1.70
influence of sorbed moisture due to the nature of the
Studies on the radical polymerization of N-vinyl 2-pyrrolidone initiated by diphenyl ditelluride 191

Table 3 ICPMS analysis report

Run Label 125 Te (ppm)

1 dsk 5 (PM) 3,731.000

2 dsk 5 (PM) 3,765.000
3 dsk 5 (PM) 1,953.000
Mean of dsk 5 (PM) 3,150.000
SD of dsk 5 (PM) 1,036.000
% RSD of dsk 5 (PM) 32.910

classified as one of those polymers for which Tg increases

Fig. 8 FTIR spectral analysis of PNVP
materials. For anhydrous NVP the Tg value is 175±1°C .
The effect of diluents and plasticizers on the Tg of a
polymer may be expressed by Eq. 3:
1 W1 W2
¼ þ
Tg Tg1 Tg2
Where the subscript 1 & 2 pertain to polymer and diluents
or plasticizers, respectively. Applied to the PNVP/H2O
system the equation becomes Eq. 4:
  
1 Tg ¼ WNVP TgNVP þ WH2 0 TgH2 0 ð4Þ
where Tg(H2O) represented the glass transition temperature
of water, W(H2O) the weight fraction of water and WNVP =
1−W(H2O). If water is homogeneously absorbed in a
polymer it effectively depressed the Tg value. The Tg water
is found to be 128 K [20], 135 K [21] and 134 K [22].
Turner and Schwartz [23] reported that Tg of a polymer
may be effected by its molecular weight. PNVP can be
with molecular weight [24, 25] towards a limiting value (of
180°C) but theoretical predictions can not yet be made for
comparison.
The presence of water during polymerization yielded
polymers of higher molecular weight was reported in the
studies of the polymerization of NVP by AIBN [26]. Tg
also get affected by stereoregularity, however, this seemed
unlikely in PNVP for two reasons. First samples of NVP
ð3Þ prepared under a variety of free radical conditions show
only minor differences in 13C-NMR spectra [27], second
the variations in stereoregularity in vinyl polymers, with the
repeat unit –CH2–CHR– (for NVP, R=pyrrolidone) have
negligible influence on the value of Tg [28].
Thermogravimetric analsysis (TGA)
The TGA curve of (Fig. 13) of the NVP exhibit weight loss
with temperature. The polymer is stable upto 380°C. The
thermal behaviour of polymer is as follows:
(a) Onset of major weight loss 380°C. Completion of
major weight loss 610°C.

1 13
Fig. 9 H-NMR spectral analysis of PNVP Fig. 10 C-NMR spectral analysis of PNVP
192 A. Tripathi, A. Srivastava

Fig. 13 TGA curve of run no. 3

Fig. 11 ESR spectrum of run no. 3 Mechanism

The addition to C–C unsaturated compounds of heteroatom

centered radicals arising from heteroatom – heteroatom
bond homolysis is one of the basic reactions in organic
(b) The total weight loss in the range of 210°C–610°C.
chemistry [31]. It is well known that organic dichalcoge-
(c) Weight losses at different temperature are:
nides eg. organic disulphides, diselenides and ditellurides
undergo photolysis or thermolysis to generate
(a) 25°C–210°C – 0–10%
corresponding organic thio, seleno and telluro radicals as
(b) 210°C–380°C – 18%
labile species [32, 33].
(c) 380°C–435°C – 62.5%
Based on above discussion the following mechanism is
(d) 435°C–610°C – 91%
suggested:

A weight loss at different stages may be attributed due to

loss of absorbed water [29] and degradation of the
backbone chain [30].

Fig. 12 DSC curve of run no. 3

Studies on the radical polymerization of N-vinyl 2-pyrrolidone initiated by diphenyl ditelluride
Conclusions
The present article reported the use of first time DPDT as
free radical initiator for the polymerization of PNVP. The
system follows ideal kinetics with activation energy 46 kJ
mol−1. The decomposition constant Kd was calculated as
1.1×10−11 s−1. This method is convenient and is useful for
the polymerization of NVP because of the simplicity of
reaction procedure.
Acknowledgement The authors are grateful to Dr. R. P. Singh,
Director, H.B.T.I., Kanpur, India, for providing necessary facilities.
The authors are also thankful to Director, IIT, Kanpur, Prof. T.M.
Aminabhavi, CEPS, Dharwad ,Karnatak for sample analysis.
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