Copolymerization of N-vinylpyrrolidone with new allyl monomers

Article abstract of DOI:10.1134/S1070427210080203

Radical copolymerization of N-vinylpyrrolidone with diallylacylhydrazines, 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride, N-allyl-2-azanorborn-5-ene, and N-allylmaleimide in the bulk and in organic solvents was studied. The kinetic features of the reactions were examined, the structures of the copolymers obtained were determined, and their physicochemical and biological properties were studied. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070427210080203

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 8, pp. 1429−1434. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.N. Gorbunova, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 8, pp. 1324−1329.
Copolymerization of N-Vinylpyrrolidone
with New Allyl Monomers
M. N. Gorbunova
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, Russia
Received February 9, 2010
Abstract—Radical copolymerization of N-vinylpyrrolidone with diallylacylhydrazines, 2,2-diallyl-1,1,3,3-
tetraethylguanidinium chloride, N-allyl-2-azanorborn-5-ene, and N-allylmaleimide in the bulk and in organic
solvents was studied. The kinetic features of the reactions were examined, the structures of the copolymers
obtained were determined, and their physicochemical and biological properties were studied.
DOI: 10.1134/S1070427210080203
Interest in purposeful synthesis of polyfunctional
polymers steadily grows. One of promising routes
to polyfunctional polymers is copolymerization of
monomers containing various functional groups. From
this viewpoint, N-vinylpyrrolidone derivatives are of
much interest. They are widely used in engineering,
medicine, production of cosmetics, pharmacy, and
agriculture [1, 2], thanks to good solubility in water
and many organic solvents, capability for complexation
with a wide range of inorganic, organic, and biological
objects, biocompatibility, and immune inertness.
tion, structure, and physicochemical properties of the
copolymers obtained. As DAHs we took N,N-diallyl-
N '-acetylhydrazine (DAAH), N,N-diallyl-N '-butanoylhy-
drazine (DABH), and N,N-diallyl-N '-benzoylhydrazine
(DABEH).
EXPERIMENTAL
N-Vinylpyrrolidone (Lancaster) was dried over KОН
and vacuum-distilled; fraction with Тb = 65°С/1.5 mm
Hg, nD20 1.5117 was used.
Diallylacylhydrazines were synthesized from
allyl chloride and the corresponding acylhydrazines
according to [9]. We used the DAAH fraction with Тb =
120°С/5 mm Hg, nD20 1.4771; DABH fraction with Tb =
145°С/8 mm Hg, nD20 1.4740; DABEH with Тm = 108°С
(acetone : water = 1 : 1).
Synthesis of polymers derived from diallyl compounds
is also a topical problem. The majority of studies in the
field of radical polymerization of allyl monomers deal
with homo- and copolymerization of N,N-dimethyl-N,N-
diallylammonium chloride. Copolymers derived from this
monomer are used as flocculants in wastewater treatment,
catalysts of a number of chemical processes, growth-
stimulating reagents, and aftertanning agents in leather
production [3–8]. Owing to such a wide spectrum of useful
properties, polymers based on nitrogen-containing allyl
compounds are unique, which makes it necessary to search
for and study new nitrogen-containing allyl monomers.
2,2-Diallyl-1,1,3,3-tetraethylguanidinium chloride
was prepared according to [10]; N-allyl-2-azanorborn-
5-ene, by the procedure described in [11]. For the po-
lymerization we used the fraction with Тb = 51–53°С
(133.3 Pa), nD20 1.4880.
N-Allylmaleimide was prepared from maleic
anhydride and allylamine according to [12]. For the
cyclization of the amido acid, instead of sodium acetate
we used iron acetylacetonate. Pure allylmaleimide was
isolated by flash chromatography (silica gel, hexane :
ethyl acetate = 90 : 10); Тm = 45°С.
This paper deals with copolymerization of N-vinylpyr-
rolidone (VP) with new allyl monomers: diallylacylhydra-
zines (DAHs), 2,2-diallyl-1,1,3,3-tetraethylguanidinium
chloride (AGC), N-allyl-2-azanorborn-5-ene (AAN), and
N-allylmaleimide (AMI). We have studied the composi-
1429

1430
GORBUNOVA
The solvents and other common chemicals after
purification by standard procedures [13] had the
in homopolymerization, but enter into copolymerization
with vinyl monomers in the presence of radical initiators.
characteristics consistent with published data.
Studies of the copolymerization of VP with DAHs,
AGC, and AAN showed that the copolymers formed are
characterized by random distribution of comonomer units
in the macromolecule, whereas the copolymerization with
AMI is characterized by high tendency of monomeric
units to alternation.
Copolymerization of VP with allyl monomers was
performed in the bulk and in solution in a vacuum in the
presence of AIBN as initiator. AIBN was recrystallized
three times from methanol and vacuum-dried at room
temperature to constant weight, Тm = 103°С (with
decomposition). The kinetics of the copolymerization
with DAHs was monitored dilatometrically [14], and
with AGC and AMI, gravimetrically. The rate V0 was
calculated from the initial portions of the kinetic curves
(up to the conversion α ≤ 5%).
The effective copolymerization constants of VP
with DAHs are given in Table 1. As can be seen, in
copolymerization of VPwith DAHs the allyl monomer is
less active. Therefore, at all the initial monomer ratios the
copolymers formed are enriched in N-vinylpyrrolidone
units.Theactivityofthemonomerscontainingfunctional
groups is noticeably affected by the medium, in
particular, by the presence of hydrogen bonds which can
be formed both between monomers, between monomers
and radicals, and between monomers and solvent. We
found that, in polymerization of VP with DABEH, the
activity of the allyl monomer in proton-donor solvents
(methanol) is higher, and that of VP, lower compared to
the polymerization in the bulk (Table 1).
The copolymers were purified by triple reprecipita-
tion from a solvent into a precipitant. The solvent/
precipitant systems were chosen individually for each
system: for copolymers of VP with DAHs and AGC,
methanol/diethyl ether; for copolymer of VP with AAN,
methanol/diethyl ether; for copolymer of VP with AMI,
chloroform/water.
The purified copolymers were dried in a vacuum at
50°С to constant weight. The composition of the copoly-
mers was calculated from the results of elemental analysis.
A study of the copolymerization of VP with AGC
showed that the allyl monomer is more active in the
process. Therefore, at all the initial monomer ratios
the copolymers formed are enriched in AGC units.
The relative activity of VP in copolymerization with
AGC in DMSO and methanol is lower compared to the
copolymerization in the bulk, which is apparently due
to formation of complexes between the propagating
macroradicals and active solvent (Table 2).
The effective copolymerization constants r1 and r2
were calculated by the Mayo–Lewis [15], Fineman–Ross
[16], and Kelen–Tüdös [17] methods.
The 13С NMR spectra were recorded on a Bruker
AM-300 spectrometer (operating frequency 75.5 MHz)
with broadband proton decoupling and in the “mono-
resonance” mode. The resolution of the analog-to-
digital converter was 0.1 Hz. As solvents we used
DMSO-d6, СDСl3, and D2О; the internal references
were tetramethylsilane and 2,2-dimethyl-2-silapentane-
5-sulfonic acid.
Data on copolymerization of VP with AAN show
that the activity of AAN in radical copolymerization is
low. In particular, in copolymerization of VP with AAN
at an equimolar monomer ratio in the initial mixture the
AAN content in the macrochain is about 10–15 mol %
(Table 3).
The intrinsic viscosity [η] (dl g–1) was determined by
viscometry with an Ubbelohde viscometer).
The acute toxicity parameters of the copolymer
samples were determined by Prozorovskii’s express
method [18].
Table 1. Effective constants of copolymerization of VP with
DAHs (М2) in bulk copolymerization (AIBN, 90°С)
The antimicrobial activity was determined by the
method of twofold serial dilutions [19] with museum
test cultures of Escherichia coli, strain 25922 and
Staphylococcus aureus, strain 906.
Monomer M2
r1
r2
r1r2
r1/r2
DAAH
DABH
DABEH
2.80 ± 0.20 0.46 ± 0.18
6.20 ± 0.28 0.20 ± 0.07
3.90 ± 0.24 0.30 ± 0.11
1.29
1.24
6.1
It is known that allyl compounds characterized
by the tendency to degradation chain transfer to the
monomer are weakly active in radical polymerization
reactions [3, 20, 21]. The previous studies showed that,
except AMI, the new monomers remain practically inert
31.0
1.17
0.99
13.0
5.9
DABEH a 2.42 ± 0.18 0.41 ± 0.14
a Copolymerization in methanol, 80°C.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 8 2010

COPOLYMERIZATION OF N-VINYLPYRROLIDONE WITH NEW ALLYL MONOMERS
1431
Table 2. Effective constants of copolymerization of VP (М1)
with AGC (AIBN, 80°С)
VP–AMI system is 1, and for the VP–DABH and VP–
AGC systems it is 1.3.
Copolymerization
r1
r2
With an increase in the content of the allyl monomer
in the initial monomer mixture in copolymerization of
VP with DAHs, AGC, and AAN, the copolymerization
rates decrease. For example, in copolymerization of VP
with AGC, an increase in the mole fraction of the allyl
monomer by a factor of 3 (from 20 to 60 mol %) leads
to a decrease in the reaction rate by a factor of 2. The
composition dependences of the initial rate of copoly-
merization of VP with DAHs (Fig. 2) show that the rate
of the copolymerization of VP with DAAH and DABEH
is higher than with DABH. The curve of the rate of co-
polymerization of VP with AMI vs. composition of the
initial monomer mixture has a maximum in the region of
50 mol % AMI (Fig. 3).
In bulk
0.92 ± 0.01
0.83 ± 0.07
0.90 ± 0.02
1.35 ± 0.12
1.80 ± 0.15
1.45 ± 0.13
In DMSO
In methanol
Table 3. Copolymerization of VP with AAN (М2) in the
bulk. [М1] : [М2] = 1 : 1, [AIBN] = 3 wt %
Copolymer composition,
Т, °С
τ, h
Yield, %
[M1]/[M2]
70
80
80
80
5
9.6
8.5
16.0
25.8
9.3/90.7
8.1/91.9
14.5/85.5
15.4/83.6
4.5
8.5
13
The dependence of the copolymer composition on
the composition of the initial monomeric mixture of VP
with AMI is shown in Fig. 1. The effective constants of
copolymerization of VP (М1) with AMI are as follows:
r1 = 0.05 ± 0.01, r2 = 0.53 ± 0.02. The data obtained
show that the copolymerization of VP with AMI is
characterized by high tendency of the monomeric units
to alternation (r1 r2 = 0.03).
The temperature dependences of the reaction rates
were studied in the range 70–90°С. The overall activa-
tion energy of the copolymerization of VP with DAHs is
78.2 ± 2.5; with AGC, 68.3 ± 1.5, and with AMI, 58.3 ±
1.5 kJ mol–1.
The structure of the copolymers obtained was
determined by 13С NMR (Table 4). Irrespective of
The kinetic studies showed that the systems under
consideration are characterized by the reaction order
of 0.5 with respect to the initiator, which is typical of
radical polymerization. This fact is indicative of the
bimolecular termination of propagating chains and
absence of degradation chain transfer to the monomer,
typical of allyl monomers [22, 23]. The reaction order
with respect to the sum of the monomers (at their
equimolar ratio) for the VP–DAAH, VP–DABEH, and
Fig. 2. Initial rate V of copolymerization of VP with DAHs (М2)
as a function of the composition of the initial monomer mixture
(mole fraction scale). DMSO, [М1 + М2] = 3.2 M, [AIBN] =
10–2 M, T = 80°C. (1) DAAH, (2) DABH, and (3) DABEH.
Fig. 1. Composition of copolymers of VP (М1) with AMI as
a function of the composition of the initial monomer mixture
(polymerization in DMF). [М1 + М2] = 1.4 M, [AIBN] =
0.03 M, T = 80°C. (M2, m2) Mole fractions of AMI in the
initial mixture and copolymer, respectively.
Fig. 3. Initial rate V of copolymerization of VP with AMI
(М2) as a function of the composition of the initial monomer
mixture (mole fraction scale). DMF, [М1 + М2] = 1.4 M,
[AIBN] = 0.03 M, T = 80°C.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 8 2010

1432
GORBUNOVA
Table 4. 13С NMR chemical shifts and multiplicities of copolymer signals a
Chemical shift δ, ppm, for indicated atoms
C1, C1' C2, C2' C3, C3' C4 C5 C6 C7 C8 C9
Iso-
mers
Structural unit of copolymer
C10 C11 C12 C13
cis- 62.25 35.08 29.14 173.5 21.45 31.85 46.25 179.8 33.67 19.95 44.76
trans- 64.85 40.63 32.14
s
q
t
48.06
d
s
t
t
t
t
d
t
I
cis- 56.80 33.85 28.86 168.5 29.45 15.95 11.90 28.78 41.42 170.8 31.46
39.75
t
trans- 58.71 33.85 30.52
s
t
t
q
t
42.12
d
s
t
t
d
t
II
cis- 59.84 39.05 30.85 163.9 135.1 127.2 128.3 131.1 29.97 41.95 164.7
16.99
t
trans- 59.02 39.85 31.06
s
d
d
d
d
t
42.63
d
s
t
d
t
III
IV
V
55.59 43.12 51.01 162.1 46.20 14.55 32.29 49.30 180.3 33.41 20.05
t
d
t
s
t
q
t
d
s
t
t
54.62
d
–
68.36 45.52 71.08 86.55 45.52 55.72 136.9 117.2 32.29
173.3
s
t
d
d
d
t
t
d
t
t
39.04 162.2 39.32 134.5 116.9 35.70 44.04 175.7 30.75 17.88 40.43
d
c
t
t
d
t
d
s
t
t
t
VI
a
In compound III, C14 gives a triplet at 44.16 ppm; in V, C14 gives a triplet at 31.46 ppm; C15, a triplet at 16.7 ppm; and C16, a triplet at
40.48 ppm.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 8 2010

COPOLYMERIZATION OF N-VINYLPYRROLIDONE WITH NEW ALLYL MONOMERS
1433
the conditions, both double bonds of DAHs and AGC
participate in the copolymerization with N-vinyl-
pyrrolidone, with the formation of five-membered
pyrrolidine and pyrrolidinium structures, respectively.
Analysis of the 13С NMR spectra of VP–DAH
copolymers shows that block fragments of the vinyl
monomer with inclusions of DAH units prevail in
the structures of the copolymers. The DAH units are
pyrrolidine rings with considerable prevalence of
cis isomers of the heterocycles over trans isomers.
Copolymerization of AAN with VP occurs via double
bond of the norbornene ring. Copolymerization of AMI
with VP in DMF occurs via double bond of maleimide.
The allyl group ofAAN andAMI under these conditions
does not participate in the copolymerization.
polymers with random distribution of the comonomeric
units in the macromolecules, whereas the copolymeriza-
tion with N-allylmaleimide yields copolymers with high
tendency of monomeric units to alternation.
(2) Both double bonds of the diallyl compounds par-
ticipate in the copolymerization with N-vinylpyrrolidone.
Copolymerization of N-vinylpyrrolidone with the nor-
bornene derivative occurs via double bond of the norborn-
ene ring, and with allylmaleimide in dimethylformamide,
via double bond of maleimide.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project no. 09-03-00220)
and by the Program of the Presidium of the Russian
Academy of Sciences “Development of Procedures for
Preparing Chemical Substances and of New Materials.”
Copolymers of VP with DAHs are soluble in
methanol, chloroform, DMSO, and DMF and insoluble
in diethyl ether, acetone, THF, ethyl acetate, benzene,
and other organic solvents. The copolymer of VP with
DAAH is also soluble in water. Copolymers of VP with
AGC are soluble in water, methanol, chloroform, DMF,
and DMSO. The intrinsic viscosity of the copolymer of
VP with DAAH (80 : 20 mol %) is 0.11 dl g–1 (water,
25°С), and that of the copolymer of VP with AGC (80 :
20 mol %), 0.16 dl g–1 (water with 0.1 N NaCl, 25°С).
The MW of the VP copolymers containing 20 mol %
DAAH or 20 mol %AGC, estimated by the Levy–Frank
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