Copolymers based on diallylhydrazines

Article abstract of DOI:10.1023/B:RJAC.0000044167.00715.3b

The possibility of preparing polymers based on N,N-diallylhydrazine derivatives by allylation of carboxylic acid hydrazides was considered.

Full text of DOI:10.1023/B:RJAC.0000044167.00715.3b

Russian Journal of Applied Chemistry, Vol. 77, No. 7, 2004, pp. 1160 1164. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 7,
2004, pp. 1174 1178.
Original Russian Text Copyright
2004 by Vorob’eva, Gorbunova, Gusev, Muslukhov, Kolesov, Tolstikov.
MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS
Copolymers Based on Diallylhydrazines
A. I. Vorob’eva, M. N. Gorbunova, V. Yu. Gusev, R. R. Muslukhov,
S. V. Kolesov, and A. G. Tolstikov
Institute of Technical Chemistry, Perm Scientific Center, Russian Academy of Sciences, Perm, Russia
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa,
Bashkorkostan, Russia
Received March 12, 2004
Abstract The possibility of preparing polymers based on N,N-diallylhydrazine derivatives by allylation
of carboxylic acid hydrazides was considered.
The range of nitrogen-containing allyl compounds
from which linear macromolecular polymers can be
produced by radical homo- and copolymerization is
very limited. Actually, only quaternary diallylammo-
nium salts are widely used as monomers for synthesis
of polyfunctional polymers [1 3]. At the same time,
such polymers exhibit unique properties [4 6], which
makes it urgent to search for and study nitrogen-con-
taining allyl monomers of new structural types. In this
respect, promising monomers are N-allylated deriva-
tives of carboxylic acid hydrazides. Hydrazides of
aliphatic acids have flotation properties [7], and hy-
drazides of naphthenic acids are selective extracting
agents for copper [8, 9].
where R is CH , C H , or C H .
3 3 7 6 5
The monomers used for the synthesis of copoly-
mers were acrylonitrile (AN), acrylamide (AA), meth-
yl methacrylate (MMA), vinyl acetate (VA), N-vinyl-
pyrrolidone (VP); the initiators were azobis(isobutyro-
nitrile) (AIBN), potassium persulfate (PP), and ben-
zoyl peroxide (BP); the solvents were methanol,
chloroform, and dimethyl sulfoxide. After purification
by common procedures, the characteristics of all
chemicals were in good agreement with published
data. Sulfur dioxide was dried by passing through
concentrated H SO and freshly calcined CaCl .
2
4
2
Copolymerization of DAHs with vinyl monomers
(VMs) was carried out in a vacuum in the bulk and in
a solution in the presence of radical initiators (for
polymerization conditions, see Table 1).
Preparation of derivatives of N,N-diallylhydrazines
(DAHs) is the way not only to produce new polyfunc-
tional polymers but also to impart to them certain
physicochemical and biological characteristics typical
for the initial compounds. The first stage on this
way is to establish the possibility of involving these
derivatives in radical polymerization.
Copolymerization of DAHs with sulfur dioxide
was carried out in a glass reactor by the procedure
described in [10] (for polymerization conditions, see
Table 2). The polymers were dried by twofold repre-
cipitation from a solvent to a precipitant chosen in-
dividually for each system. The purified polymers
were dried in a vacuum at 50 C to constant weight.
The compositions of copolymers were evaluated from
Here we attempted to prepare polymers based on
DAHs, in particular, N,N-diallyl-N -acylhydrazine
(DAAH), N,N-diallyl-N -propanoylhydrazine (DAPH),
and N,N-diallyl-N -benzoylhydrazine (DABH).
13
the results of elemental analysis. The C NMR spec-
tra were recorded on a Bruker AM-300 spectrometer
EXPERIMENTAL
operating at 75.46 MHz. DMSO-d and D O were
6
2
used as solvents, and tetramethylsilane and DSS, re-
spectively, as internal references. The UV spectra were
recorded on a Shimadzu UV-VIS-NIR 3100 spectro-
photometer. The composition of the complex was
determined by the method of isomolar series [11].
N,N-Diallylhydrazines were synthesized by the
reaction of hydrazides of aliphatic and aromatic acids
with allyl halides (AllHlg):
R CO NH NH2 + 2AllHlg
+ 2HHlg,
R CO NH N(All)2
Under usual conditions, DAHs practically do not
enter into homopolymerization by a free-radical mech-
1070-4272/04/7707-1160 2004 MAIK Nauka/Interperiodica

COPOLYMERS BASED ON DIALLYLHYDRAZINES
1161
Table 1. Copolymerization of diallylhydrazine derivatives (M1) with VMs (M2) [AIBN] = 3.0 wt %, T = 90 C
Composition of initial
mixture, mol %
Copolymer com-
position, mol %
Yield,
%
M1
M2
Medium
Solvent for copolymers
M1
M2
m1
m2
DAAH MMA
DAAH AN
DAAH AA
DAAH VA
DAAH VP
50.0
66.6
50.0
57.9
50.0
64.4
50.0
65.7
50.0
55.0
50
50.0
33.4
50.0
42.1
50.0
35.6
50.0
34.3
50.0
45.0
50
In the bulk
31.5
12.8
18.0
12.8
41.0
21.0
11.0
3.0
18.3
23.0
14.2
25.0
20.3
28.0
38.0
81.7
73.0
85.8
75.0
79.7
72.0
62.0
DMSO, methanol, acetone,
benzene, THF, chloroform
DMSO, DMF, pyridine
H2O*
Methanol
In the bulk
DMSO, H2O
DMSO, methanol, acetone
H2O, methanol, acetone
DMSO
28.2
10.0
27.2
19.0
15.0
81.0
85.0
DAAH Acrylic
acid
DABH AN
DABH AA
34
33
66
37
Methanol
29.3
38.2
10.2
10.5
89.8
89.5
DMSO, DMF, pyridine, acetone
Insoluble
* Potassium persulfate initiator.
Table 2. Copolymerization of diallylhydrazine derivatives (M1) with SO2. Composition of the initial mixture:
M1 : M2 = 1 : 1; [In] = 3.0 wt %, T = 90 C
Copolymer composition, %
M1
Medium
Initiator
Yield, %
Solvent for copolymer
DMSO, water
m1
m2
DAAH
In the bulk
AIBN
AIBN*
BP
PP
AIBN
AIBN
41.7
48.2
5.6
38.5
50.2
60.0
48.0
49.0
47.0
47.0
53.0
48.0
52.0
51.0
53.0
53.0
47.0
52.0
Aqueous
Acetone
Chloroform
DAPH
DABH
In the bulk
Chloroform
Methanol
DMSO
Chloroform
AIBN
AIBN
AIBN**
AIBN**
AIBN**
50.0
70.4
34.3
44.4
57.4
49.0
48.0
49.0
50.0
48.0
51.0
52.0
51.0
50.0
52.0
DMSO, methanol
DMSO, DMF
In the bulk
Methanol
AIBN
AIBN
23.1
35.5
49.0
50.0
51.0
50.0
* In the presence of HCl.
** Polymerization duration 1 h.
anism. The activity of DAHs somewhat increases on
adding protic and aprotic acids, which is a well-
known procedure for activation of allyl monomers.
However, in this case, e.g., in polymerization of
DAAH in the presence of HCl, H PO , and ZnCl at
the ratio DAH : acid = 1 : 1.2 (T = 90 C, initiator
AIBN, 30 h), the yield of the homopolymer did not
exceed 6 10%.
The use of DAHs in radical copolymerization with
VMs containing both electron-acceptor (AA, AN, and
methacrylic acid) and electron-donor (VA and VP)
substituents is significantly more efficient. Copoly-
merization of DAHs (M ) with vinyl monomers (M )
proceeds at a noticeable rate at a temperature above
80 C and initiator concentration of no less than
2.5 wt %. DAHs are less active than vinyl monomers.
3
4
2
1
2
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 7 2004

1162
VOROB’EVA et al.
polymers in copolymerization in the bulk do not ex-
ceed 50% even at extremely long reaction time (up to
10 h). In copolymerization in a solution, the yield
of copolymer depends on the solvent. In particular, in
chloroform the yields of DAPH copolymers are higher
than those in the bulk and can reach 70%.
The structure of the copolymers was determined
13
by C NMR. In the spectra of copolymers (Table 3)
of derivatives of DAHs with SO (nos. 6 8), along
2
with the signals of substituent atoms at the NHR
group, where R is CH , C H , and C H , there are
, nm
3
3
7
6 5
only three pairs of signals corresponding to two
methylene and one methine groups of the polymer
chain, which are stereoisomeric. This suggests the
structural homogeneity of the copolymers. Two pairs
of low-field triplets correspond to cis/trans stereo-
Electronic absorption spectra of solutions in chloroform.
(D) Optical density and ( ) wavelength. (1) DAAH
1
3
([DAAH] 1 10
M), (2) SO ([SO ] 1 10
M),
2
2
3
(3) a mixture of DAAH and SO ([DAAH] 5 10 M,
[SO ] 5 10 M), and (4) difference of spectrum 3 and
half-sum of spectra 1 and 2.
2
4
2
1
1
3 3
isomeric carbon atoms C C and C C ; two doublet
2
2
signals correspond to stereoisomeric C and C atoms
of the heterocycle. The relative content of cis/trans
stereoisomeric units of DAH was estimated from the
Copolymers of all the monomer pairs are enriched
with VM units as compared to the composition of the
initial mixture (Table 1). At the equimolar ratio of the
monomers in the initial mixture, the content of DAHs
in the copolymers (excluding the copolymer with VA)
does not exceed 20 mol %.
13
C NMR spectrum to be approximately 4/1. The
chemical shifts of the above carbon atoms, consider-
ing the additive effect of substituents, SO
NH R groups, are close to the chemical shifts of the
and
2
In spite of high temperature (90 C) and high ini-
tiator concentration (3 wt %), the rate of copolymeri-
zation of DAHs with VM is low, especially at the
corresponding atoms of the copolymer of N,N-dimeth-
yl-N,N-diallylammonium chloride with SO [10].
2
The chemical shifts of VM units in the spectra of the
copolymers are practically the same as those for the
corresponding carbon atoms of their homopolymers
[12 16]. In the spectra of the copolymers with broad-
band proton decoupling, similarly to the spectra of
VM homopolymers, there are configuration multiplets
content of M in the reaction mixture exceeding
1
50 mol %.
DAHs are significantly more active in copolymeri-
zation with sulfur dioxide having high electron-
acceptor power. All the DAHs copolymerize with SO
to form alternating copolymers with equimolar com-
position, irrespective of the ratio of the monomers in
the initial mixture, solvent and initiator nature, and
reaction temperature (Table 2). The constancy of the
composition of the copolymers, irrespective of the
ratio of the monomers in the reaction mixture, sug-
2
7
belonging to pseudo-asymmetric C atom and adjacent
and
carbon nuclei. These data suggest that the
copolymer contains VM blocks alternating with sepa-
rate DAH units.
The resulting copolymers are soluble in polar
solvents such as DMSO and DMF. Copolymers of
gests that copolymerization of DAHs with SO pro-
2
ceeds with formation of complexes [DAH SO ].
DAAH with SO , AA, and VP are also soluble in
2
2
The UV spectra of a mixture of DAAH with SO in
water. Preliminary tests showed that copolymers of
2
chloroform contain a new band of charge transfer with
DAAH with SO have flocculation properties, in par-
2
= 263 nm (for SO ,
= 275.9 nm),
ticular, in precipitation of Cu(OH) .
max
2
max
2
suggesting formation of a donor acceptor complex
(see figure).
CONCLUSIONS
The reaction conditions do not affect the composi-
tion of copolymers but significantly affect the co-
polymer yield (Table 2). In particular, higher yields of
(1) Derivatives of diallylhydrazines are a new
structural type of N-allylated monomers promising for
production of polyfunctional polymers, among them
water-soluble, in radical polymerization.
copolymers of DAH with SO were obtained with
2
AIBN and PP as an initiator; with BP, there was vir-
tually no copolymerization.
(2) Diallylhydrazines enter into copolymerization
reactions with participation of both double bonds to
In the systems under consideration, the yields of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 7 2004

COPOLYMERS BASED ON DIALLYLHYDRAZINES
Table 3. Chemical shifts and multiplicity of the signals in the 13C NMR spectra of copolymers
Copoly- Stereo-
1163
C11
C1, C1 C2, C2 C3, C3
C4
C5
C6
C7
C8
C9
C10
mer no. isomer
1
2
cis
trans
62.20
62.35
t
40.19
40.88
d
28.09 175.04 21.69
28.41 174.75
36.19
37.14
36.82
t
32.56
32.88
t
44.40
44.18
43.82
d
27.86
27.38
26.72
d
182.09
183.05
s
q
t
s
cis
trans
58.96
60.08
t
39.69
41.53
d
25.44 173.71 21.17
28.73 173.58 19.62
120.28
120.83
121.94
s
t
s
q
3
4
cis
trans
58.76
59.32
t
59.98
62.81
t
34.80
36.05
d
40.25
43.41
d
34.91
35.63
d
29.76 176.74 21.16
43.85
t
44.38
s
19.47
18.45
q
170.15
169.87
s
177.15 51.60
32.77
t
s
q
176.17
s
q
cis
trans
27.30 178.30 20.40
32.80
31.94
t
66.51
69.31
72.19
d
21.12
19.48
q
29.94
s
q
t
32.77
35.44
t
5
cis
trans
62.25
64.85
t
35.08 29.14
40.63 32.14
173.54 21.45
31.85
t
46.25
48.06
d
179.78
s
33.67
t
19.95 44.76
s
q
t
t
d
t
cis
trans
38.13
41.05
d
6
7
8
cis
trans
61.90
61.33
t
57.80
58.35
t
57.41
58.04
t
35.41
37.82
d
33.53
36.51
d
33.27
33.27
d
54.01 177.13 22.42
57.02
t
s
q
cis
trans
52.19 165.51 133.09 127.45 128.55 131.83
55.45
t
s
s
d
d
d
cis
trans
52.09 170.73 35.58
18.50
t
13.45
q
55.26
t
s
t
3
1
3
2
3
7
6
8
CH
3
7
3’
1’
3
7
3
3
6
7
3
2
2
2
2
6
m
2
2’
2
3
1
3
n
6
6
7
2
2
m
m
CH CH
2
m
n
1
1
n
n
m N
1
1
1
1
C=O
n
C N
O
1
8
8
8
NH
O
N
N
N
9
N
2
C
11
C
O
N
C
8
O
O
no. 2
NH
NH
CH
no. 1
NH
NH
10
9
3
9
NH
no. 3
CH
CH C=O
10
3
no. 5
O
CH C=O
3
3
CH C=O
CH C=O
3
no. 4
C
5
5
4
3
3
4
5
4
5
5
4
4
CH
3
3
3
1
3
3
3
2
2
2
2
2
2
SO
7
.
2
n
SO
n
SO
n
2
2
1
1
1’
1
1
N
N
N
NH
CH C=O
NH
NH
no. 6
6
no. 7
no. 8
3
O
C
6
O=C
8
3
4
5
4
5
4
CH
7
5
6
7
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 77 No. 7 2004

1164
VOROB’EVA et al.
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