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Polybenzimidazoles containing methyl groups in the azole ring
Polybenzimidazoles containing methyl groups in azole ring
2117
(2) A study was made of the properties of copolymers of ethylene with the diallyl ester of methylphosphinic acid of different compositions and molecular weights. It was found that the density, melting point, solubility, crosslinking ability and mechanical properties of copolymers depend on the content of units of the diallyl ester of methylphosphinic acid. Translated by E. SEMERE REFERENCES 1. M. Kh. ATAKAZOVA, V. I. GUSEV, Ye. V. KUZNETSOV, V. N. MONASTYRSKH and R. A. TERTERYAN, T r u d y K K h T I ira. Sin. Kirova, 36, p. 381, 1967 2. V. A. KARGIN, M. B. KONSTANTINOPOL'SKAYA, R, A. TERTERYAN and Z. Ya. BERESTNEVA, Dokl. AN SSSR 164: 112, 1965 3. S. G. LYUBETSKII, Zh. prikl, khimii 35: 141, 1962 4. R. A. TERTERYAN, Yu. I. BARASH and L. N. SHAPKINA, Vysokomol. soyed. A1O: 1673, 1968 (Translated in P o l y m e r Sei. U.S.S.R. 1O: 7, 1940, 1968) 5. R. A. TERTERYAN, Vysokomol. soyed. A l 1 : 1789, 1969 (Translated in Polymer Sci. U.S.S.R. 11: 8, 1969) 6. N. FEINEMAN and S. ROSS, J. Polymer Sei. 5: 259, 1950 7. G. A. MORTIMER, J. Polymer Sci. B3: 343, 1965 8. F. E. BROWN and G. E. HAM, J. Polymer Sei. A2: 3623, 1964
POLYBENZIMIDAZOLES CONTAINING METHYL GROUPS IN THE AZOLE RING* V. V. KORSHAK, M. M. TEPLYAKOV a n d R . D . FEDOROVA I n s t i t u t e of Hetero-organic Compounds, U.S.S.R. A c a d e m y of Sciences D. I. Mendeleyev Chemico-technological Institute, Moscow
(Received 20 September 1968)
WE H A V E previously described [1] polybenzimidazoles containing methyl groups in the benzene nucleus. It was pointed out that the addition of these substituents to the aromatic ring considerably improves the solubility and reduces the brittlness of polymers without significantly lowering their heat resistance. In our view it was of interest to investigate further the effect on properties of methyl substituents in polybenzimidazoles. Therefore, we attempted to synthesize polybenzimidazoles with methyl substituents on the nitrogen atom of the imidazole ring and synthesize polybenzimidazoles containing methyl substituents in the benzene and imidazole rings at the same time. * Vysokomol. soyed. A l l : No. 8, 1858-1862, 1969.
2118
V.V. KORSH~ et al.
It might be expected that these polymers will have a more satisfactory solubility and higher elasticity as a consequence of a weakening of molecular interaction on adding these substituents. When we started our investigation there was only one report in the literature [2] concerning the synthesis of polybenzimidazoles with a methyl substituent at the nitrogen atom of the imidazole ring; the results obtained by the authors did not lead to any conclusion concerning the effect of this substituent on the variation of properties of the polymer. As the initial tetra-amines we synthesized bis-(3-amino-4-N-methylaminophenyl)methane (I), 3,3'-diamino-N,N'-dimethyltolidino (II) and bis-(3-amino4-lg-methylamino-5-methylphenyl)methane (III), not described in the literature, which by polyheterocyclization with the diphenyl esters of several dicarboxylic acids were converted to the corresponding polybenzimidazoles by the scheme: RCI-I~Ntt-~
R, (~V--NHCII8
where R' =CH~ or is absent; R"----H, CH3,
The main properties of polybcnzimidazoles synthesized by the authors are given in Table 1. The Table indicates that nil the polymers except those based on terephthalic acid (polymers 2, 6 and 10) of fairly high molecular weight (which is proved by the kinematic viscosity values) are readily soluble in several different organic solvents. The satisfactory solub'lity of the polybenzimidazoles synthesized is apparently due to reduction in packing density and a weakening of inter-chain reaction as a result of the addition (~f lateral substituents. Polybenzimidazoles simultaneously containing methyl s:~bstitu(,nts in the benzene nucleus and azole ring have the most satisfactory solubilities. Thermogravimetric analytical data indicate (Fig. la and Table 1) that polybenzimidazoles based on aromatic acids have fairly high heat resistance, decomposition beginning in air only at a temperature of the order of 400 ° and higher; polymers from terephthalic acid (polymers 2, 6 and 10) have the highest heat resistance of the three tetra-amines taken. It should be noted that the addition of methyl substituents to the azole ring of polybenzimidazole does not markedly reduce the heat resistance, compared with the corresponding tinsubstituted polybenzimidazole. Thus, polymer 1
Polybenzimidazoles containing methyl groups in azole ring
2119
(Table 1) containing a methyl group at the nitrogen atom has an initial decomposition temperature of 450 ° and the corresponding polybenzimidazole, without a methyl group, 490 ° [3].
b
o~ I00I "; 0
y
f
3
.~ 20~
~o
l
i
200
i
II
4,O0
800 T,°C
100
2OO
300
2
I
I
#00
T, °C
Fro. 1. Thermogravimetric (a) and temperature deformation curves (b) of poly-Nmethylbenzimidazoles: /--polymer 2, 2--polymer 1, 3--polymer 10, 4--polymer 9. Temperature/deformation curves shown in Fig. lb indicate a certain reduction in heat resistance on adding methyl groups to the azole ring of the polymer chain. Thermomechanical tests of films (Fig. 2) show that substituents in the benzene nucleus and particularly in the azole ring lower the glass transition temperature
8,%
100
200
300 4`00 T, °C
FIG. 2. Thermomechanieal tests of polybenzimidazole films: 1--copolymer of 2,2'(m-phenylene, p,p-diphenyloxide)-6,6'-dibenzimidazolylmethane; 2--poly-2,2'(m-phenylene) -4,4'-dimethyl-6,6'-dibenzimidazolylmethane; 3 -- poly- 1, l'-dimethyl2,2'- (m-phenylene) -6,6'-dibenzimidazolylmethane. under a given load (100 kg/cm~). To investigate the effect of substitution on the variation of mechanical properties, particularly on the reduction of brittleness of the polybenzimidazoles, we examined films obtained b y pouring the solution of some of the synthetic polymers into dimethylsulphoxide. Table 2 indicates the properties of unoriented films. It is apparent from Table 2 that N-methyl-substituted polybenzimidazoles can form fairly elastic films. Polymer films based on diphenylisophthalate are the strongest. General relations in the variation of the properties, including the mechanical properties of films, according to the presence and position of methyl substituents, have previously been described b y the authors [3].
2120
V,V. K o ~ s m u ~ a / .
As the properties and mainly the heat resistance of polybenzimidazoles can be greatly affected b y structure, e.g. incomplete "ring formation~ finding the conditions of synthesis to ensure complete ring closure is very important. N-Alkyl-substituted polybenzimidazoles are a very convenient means of investigating the degree of polycyclization, since with complete ring formation in the polymer chain the absence of an amide atom of hydrogen can be easily established
~=
I
6"0
I
!
#.0 2-O I
I
I
c~,p p.m.
Fie. 3. PMR spectra of polymers: /--initial tetra-amlne; 2--reaction temperature 270°, duration 5 hr; 3--temperature 270°, 10-s ram, duration 5 hr; 4--temperature 300°, 10- s - 10-e ram, duration 5 hr. b y proton magnetic resonance (PM~). Figure 3 illustrates the Pl%IR spectra of poly-N-methylbenzimidazole, heated under various conditions. A variation in the chemical shift intensity of the amide proton according to heating time and the nature of the process proves that ring formation is complete when the last stages of the process are carried out under very rigorous conditions: 300-350 ° , a pressure of 10-3-10-emm heating time of 5-10 hr (curve d). When ring formation takes place under milder conditions the amide bonds (curves 2, 3) are retained in the polymer and m a y become the weak units when the polymers are used at high temperatures.
III
12
1 '09 0.99
isophthalic therephthalic 4,4'-dicarboxydiphenyloxide i s o p h t h a l i c , 4,4'-dicarboxydiphenyloxidc
t Molar ratio of initial diestcrs 0.3 : 0'7, respectively.
0.62
0"58
0-60
0'62
0-82 0-63 0"66
205
210
300 230 245
320
0.88
0-95
0-86 0'65 0"70
335 345
340 310
0-98 0"90
0'76 0'78
350 380
0.95
1'00
in dimethylsulphoxide
380
400
410 390-400 410
410-420
410 450
450 440-450
450 480-490
formamide
dimethyl
ps
S
ps
S
S
ps
ps
S
S
ps
ps
benzyl alcohol
S
ps
S
"
pyridine
S o l u b i l i t y in *
S
ps
S
noIle
cyelohexa-
POLYBENZIMIDAZOLES
Temperatur e of i n i t i a l Softening intensive point, decomoC position, °C
OF I~-SUBSTITUTED
0-80 0.82
0-95
1"05
in 1-IsSO4
acid d i p h e n y l e s t e r
isophthalic terephthMio 4,4-dicarboxydiphenyloxide i s o p h t h a l i e , 4,4'-dicarboxydiphenyloxide t isophthalie terephthalic 4,4'-dicarboxydiphenyloxide isophthalie,4,4'-dicarboxydiphenyloxide
PROPERTIES
Kinematic viscosity, dl/g
FUNDAMENTAL
* s--Polymer is fully soluble, ps-partially soluble, i--insoluble,
9
10 11
II
II II II
tetraamine
III III III
Polymer No.
Initial compounds
TABLE 1.
S
ps
S
S
S
ps
s
S
S
ps
ps
trieresol
t~ ~.~
5' gQ
N
~0
o
~q
5"
~0
o
o
S
V . V . KORSHAK et aL
2122
T A B L E 2. ~ I E C H A N I C A L P R O P E R T I E S OF U N O R I E N T ~ D P O L Y -N - M E T H Y L B E I ~ Z I M I D A Z O L E F I L ~ S
Polymer, No.*
Tensile strength, kg/cm ~
600 500 400
Breaking elongation,
%
[ I
30
40 45
* See Table 1
EXPERIMENTAL The initial diamines were obtained by the Fisher and Busch [4] method from the corresponding dinitrodiamines and methyl iodide, Subsequent reduction was carried out by the description given in a former study [5]. Bis-(3-amino-4-N-methylaminophenyl)methane is a white crystalline powder, m.p. 127-128 ° . Found, ~: C 70.04; H 7.72; N 21"90. C15H~0N4. Calculated, ~ : C 70.32; H 7.79; N 2i.81. 3.3'-Diamino-bis-~q-methylolidine, m.p. 133-134 °. Found, Yo: C 71.33; H 8.15; N 20.67. CleI-I~2N~. Calculated, ~ : C 71.07; H 8.20; N 20.72. Bis-(3-amino-4-N-methylamino-5-methylphenyl)methane, m.p. 145-146 °. Found, ~ : C 71.71; H 8.54; N 19.81. C17H~4N4. Calculated, ~ : C 71"79; H 8.48; N 19.70. The melting points of the diphenyl esters of dicarboxylic acids used were in accordance with literature data [6, 7]. The polybenzimidazoles were synthesized and their properties determined by methods described in a former report [8]. The authors are grateful to E. I. Fedin for interpreting the PNIR spectra and A. I. Mzhel'skii for carrying out the thermomechanical tests of films.
CONCLUSIONS
[ T~
(1) P o l y b e n z i m i d a z o l e s containing m e t h y l g r o u p s in t h e azole ring a n d s i m u l t a n e o u s l y in t h e azole a n d benzene rings were s y n t h e s i z e d a n d studied. (2) I t w a s p o i n t e d o u t t h a t t h e a d d i t i o n o f a l k y l g r o u p s to t h e azole ring p r o d u c e s p o l y b e n z i m i d a z o l c s of fairly high h e a t resistance a n d s a t i s f a c t o r y solubility in m a n y organic s o l w n t s a n d c a p a b l e of f o r m i n g strong elastic films. (3) P N [ R r e v e a l e d conditions for c o m p l e t e ring f o r m a t i o n d u r i n g t h e synthesis o f poly- ~q-methylbenzimidazoles. Translated by E. S E ~ R E REFERENCES
1. V. V. KORSHAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Vysokomol soyed. B9: 767, 1967 (Not translated in Polymer Sei. U.S.S.R.) 2. K. MITSUHASHI and C. S. MARVEL, J. Polymer Sci. A3: 1661, 1965 3. V. V. KORSHAK, M. M. TEPLYAKOV, R. D. FEDOROVA and Yu. Ye. DOROSHENKO, Trudy MKhTI, 57, p. 201, 1968.
New method for synthesis of cellulose chloroacetates and aminoacetates
2123
4. O. FISHER and M. BUSCH, Ber. 24; 2682, 1891 5. V. V. KORSKAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Auth. Cert. No. 218898, 1968; Byull. izobret., No. 30, 188, 1968 6. L. SCHEDER, Ber. 7: 707, 1874 7. T. M. FRUNZE, V. V. KORSHAK, A.A. IZYNEYEV and V. V. KURASHEV, Vysokomol, soyed. 7 285, 1965 (Translated in Polymer Sci. U.S.S.R. 7: 2. 313, 1965) 8. V. V. KORSHAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Izv. VUZov, Khimiya i khimich, tekhnologiya 12: 193, 1969
NEW METHOD FOR THE SYNTHESIS OF CELLULOSE CHLOROACETATES AND AMINOACETATES* t A. A. KHIDOYATOVand Z. A. Rooovnv Moscow Textile Institute
(Received 21 October 1968)
CELLULOSE derivatives and esters containing amino-groups are of considerable scientific and technological interest. These materials can be easily dyed with acid dyes and can be used as anion-exchange materials [1]. Despite the extensive possibilities for improving the properties of cellulose and cellulose esters by synthesis of amino-derivatives, except for a few publications [2-5] there have been no systematic investigations carried out in this direction. Therefore developing methods for the synthesis of cellulose esters containing amino-groups and the investigation of their properties are of considerable interest. We studied the possibility of synthesizing these cellulose esters by conversion of previously synthesized cellulose ehloroacetates. Cellulose chloroacetates can be synthesized by the reaction of cellulose with monochloroacetie anhydride [6, 7] or by esterification of partially saponified acetylcellulose with monochloroacetic acid using a basic catalyst [8]. We considered it better to investigate the possibility of synthesizing these cellulose derivates by the reaction of cellulose with monochloroacetic acid chloride. According to literature data [9, 10], acetylation of cellulose by acetyl chloride with pyridine takes place via the stage of acetyl pyridinium chloride formation. Experiments show that on mixing equimolar quantities of pyridine and monochloroacetic acid chloride or valeric acid chloride a complex is formed which precipitates as a residue: ~+RCH~COCI~ N
~/
~,
RCH~COiW+C1-
where R = - - H , - - CI, -CH~CH2CH 3. * Vysokomol. soyed. A l l : No. 8, 1863-1866, 1969. ~f R. Yegorova took part in the experimental part of the study.
2117
(2) A study was made of the properties of copolymers of ethylene with the diallyl ester of methylphosphinic acid of different compositions and molecular weights. It was found that the density, melting point, solubility, crosslinking ability and mechanical properties of copolymers depend on the content of units of the diallyl ester of methylphosphinic acid. Translated by E. SEMERE REFERENCES 1. M. Kh. ATAKAZOVA, V. I. GUSEV, Ye. V. KUZNETSOV, V. N. MONASTYRSKH and R. A. TERTERYAN, T r u d y K K h T I ira. Sin. Kirova, 36, p. 381, 1967 2. V. A. KARGIN, M. B. KONSTANTINOPOL'SKAYA, R, A. TERTERYAN and Z. Ya. BERESTNEVA, Dokl. AN SSSR 164: 112, 1965 3. S. G. LYUBETSKII, Zh. prikl, khimii 35: 141, 1962 4. R. A. TERTERYAN, Yu. I. BARASH and L. N. SHAPKINA, Vysokomol. soyed. A1O: 1673, 1968 (Translated in P o l y m e r Sei. U.S.S.R. 1O: 7, 1940, 1968) 5. R. A. TERTERYAN, Vysokomol. soyed. A l 1 : 1789, 1969 (Translated in Polymer Sci. U.S.S.R. 11: 8, 1969) 6. N. FEINEMAN and S. ROSS, J. Polymer Sei. 5: 259, 1950 7. G. A. MORTIMER, J. Polymer Sci. B3: 343, 1965 8. F. E. BROWN and G. E. HAM, J. Polymer Sei. A2: 3623, 1964
POLYBENZIMIDAZOLES CONTAINING METHYL GROUPS IN THE AZOLE RING* V. V. KORSHAK, M. M. TEPLYAKOV a n d R . D . FEDOROVA I n s t i t u t e of Hetero-organic Compounds, U.S.S.R. A c a d e m y of Sciences D. I. Mendeleyev Chemico-technological Institute, Moscow
(Received 20 September 1968)
WE H A V E previously described [1] polybenzimidazoles containing methyl groups in the benzene nucleus. It was pointed out that the addition of these substituents to the aromatic ring considerably improves the solubility and reduces the brittlness of polymers without significantly lowering their heat resistance. In our view it was of interest to investigate further the effect on properties of methyl substituents in polybenzimidazoles. Therefore, we attempted to synthesize polybenzimidazoles with methyl substituents on the nitrogen atom of the imidazole ring and synthesize polybenzimidazoles containing methyl substituents in the benzene and imidazole rings at the same time. * Vysokomol. soyed. A l l : No. 8, 1858-1862, 1969.
2118
V.V. KORSH~ et al.
It might be expected that these polymers will have a more satisfactory solubility and higher elasticity as a consequence of a weakening of molecular interaction on adding these substituents. When we started our investigation there was only one report in the literature [2] concerning the synthesis of polybenzimidazoles with a methyl substituent at the nitrogen atom of the imidazole ring; the results obtained by the authors did not lead to any conclusion concerning the effect of this substituent on the variation of properties of the polymer. As the initial tetra-amines we synthesized bis-(3-amino-4-N-methylaminophenyl)methane (I), 3,3'-diamino-N,N'-dimethyltolidino (II) and bis-(3-amino4-lg-methylamino-5-methylphenyl)methane (III), not described in the literature, which by polyheterocyclization with the diphenyl esters of several dicarboxylic acids were converted to the corresponding polybenzimidazoles by the scheme: RCI-I~Ntt-~
R, (~V--NHCII8
where R' =CH~ or is absent; R"----H, CH3,
The main properties of polybcnzimidazoles synthesized by the authors are given in Table 1. The Table indicates that nil the polymers except those based on terephthalic acid (polymers 2, 6 and 10) of fairly high molecular weight (which is proved by the kinematic viscosity values) are readily soluble in several different organic solvents. The satisfactory solub'lity of the polybenzimidazoles synthesized is apparently due to reduction in packing density and a weakening of inter-chain reaction as a result of the addition (~f lateral substituents. Polybenzimidazoles simultaneously containing methyl s:~bstitu(,nts in the benzene nucleus and azole ring have the most satisfactory solubilities. Thermogravimetric analytical data indicate (Fig. la and Table 1) that polybenzimidazoles based on aromatic acids have fairly high heat resistance, decomposition beginning in air only at a temperature of the order of 400 ° and higher; polymers from terephthalic acid (polymers 2, 6 and 10) have the highest heat resistance of the three tetra-amines taken. It should be noted that the addition of methyl substituents to the azole ring of polybenzimidazole does not markedly reduce the heat resistance, compared with the corresponding tinsubstituted polybenzimidazole. Thus, polymer 1
Polybenzimidazoles containing methyl groups in azole ring
2119
(Table 1) containing a methyl group at the nitrogen atom has an initial decomposition temperature of 450 ° and the corresponding polybenzimidazole, without a methyl group, 490 ° [3].
b
o~ I00I "; 0
y
f
3
.~ 20~
~o
l
i
200
i
II
4,O0
800 T,°C
100
2OO
300
2
I
I
#00
T, °C
Fro. 1. Thermogravimetric (a) and temperature deformation curves (b) of poly-Nmethylbenzimidazoles: /--polymer 2, 2--polymer 1, 3--polymer 10, 4--polymer 9. Temperature/deformation curves shown in Fig. lb indicate a certain reduction in heat resistance on adding methyl groups to the azole ring of the polymer chain. Thermomechanical tests of films (Fig. 2) show that substituents in the benzene nucleus and particularly in the azole ring lower the glass transition temperature
8,%
100
200
300 4`00 T, °C
FIG. 2. Thermomechanieal tests of polybenzimidazole films: 1--copolymer of 2,2'(m-phenylene, p,p-diphenyloxide)-6,6'-dibenzimidazolylmethane; 2--poly-2,2'(m-phenylene) -4,4'-dimethyl-6,6'-dibenzimidazolylmethane; 3 -- poly- 1, l'-dimethyl2,2'- (m-phenylene) -6,6'-dibenzimidazolylmethane. under a given load (100 kg/cm~). To investigate the effect of substitution on the variation of mechanical properties, particularly on the reduction of brittleness of the polybenzimidazoles, we examined films obtained b y pouring the solution of some of the synthetic polymers into dimethylsulphoxide. Table 2 indicates the properties of unoriented films. It is apparent from Table 2 that N-methyl-substituted polybenzimidazoles can form fairly elastic films. Polymer films based on diphenylisophthalate are the strongest. General relations in the variation of the properties, including the mechanical properties of films, according to the presence and position of methyl substituents, have previously been described b y the authors [3].
2120
V,V. K o ~ s m u ~ a / .
As the properties and mainly the heat resistance of polybenzimidazoles can be greatly affected b y structure, e.g. incomplete "ring formation~ finding the conditions of synthesis to ensure complete ring closure is very important. N-Alkyl-substituted polybenzimidazoles are a very convenient means of investigating the degree of polycyclization, since with complete ring formation in the polymer chain the absence of an amide atom of hydrogen can be easily established
~=
I
6"0
I
!
#.0 2-O I
I
I
c~,p p.m.
Fie. 3. PMR spectra of polymers: /--initial tetra-amlne; 2--reaction temperature 270°, duration 5 hr; 3--temperature 270°, 10-s ram, duration 5 hr; 4--temperature 300°, 10- s - 10-e ram, duration 5 hr. b y proton magnetic resonance (PM~). Figure 3 illustrates the Pl%IR spectra of poly-N-methylbenzimidazole, heated under various conditions. A variation in the chemical shift intensity of the amide proton according to heating time and the nature of the process proves that ring formation is complete when the last stages of the process are carried out under very rigorous conditions: 300-350 ° , a pressure of 10-3-10-emm heating time of 5-10 hr (curve d). When ring formation takes place under milder conditions the amide bonds (curves 2, 3) are retained in the polymer and m a y become the weak units when the polymers are used at high temperatures.
III
12
1 '09 0.99
isophthalic therephthalic 4,4'-dicarboxydiphenyloxide i s o p h t h a l i c , 4,4'-dicarboxydiphenyloxidc
t Molar ratio of initial diestcrs 0.3 : 0'7, respectively.
0.62
0"58
0-60
0'62
0-82 0-63 0"66
205
210
300 230 245
320
0.88
0-95
0-86 0'65 0"70
335 345
340 310
0-98 0"90
0'76 0'78
350 380
0.95
1'00
in dimethylsulphoxide
380
400
410 390-400 410
410-420
410 450
450 440-450
450 480-490
formamide
dimethyl
ps
S
ps
S
S
ps
ps
S
S
ps
ps
benzyl alcohol
S
ps
S
"
pyridine
S o l u b i l i t y in *
S
ps
S
noIle
cyelohexa-
POLYBENZIMIDAZOLES
Temperatur e of i n i t i a l Softening intensive point, decomoC position, °C
OF I~-SUBSTITUTED
0-80 0.82
0-95
1"05
in 1-IsSO4
acid d i p h e n y l e s t e r
isophthalic terephthMio 4,4-dicarboxydiphenyloxide i s o p h t h a l i e , 4,4'-dicarboxydiphenyloxide t isophthalie terephthalic 4,4'-dicarboxydiphenyloxide isophthalie,4,4'-dicarboxydiphenyloxide
PROPERTIES
Kinematic viscosity, dl/g
FUNDAMENTAL
* s--Polymer is fully soluble, ps-partially soluble, i--insoluble,
9
10 11
II
II II II
tetraamine
III III III
Polymer No.
Initial compounds
TABLE 1.
S
ps
S
S
S
ps
s
S
S
ps
ps
trieresol
t~ ~.~
5' gQ
N
~0
o
~q
5"
~0
o
o
S
V . V . KORSHAK et aL
2122
T A B L E 2. ~ I E C H A N I C A L P R O P E R T I E S OF U N O R I E N T ~ D P O L Y -N - M E T H Y L B E I ~ Z I M I D A Z O L E F I L ~ S
Polymer, No.*
Tensile strength, kg/cm ~
600 500 400
Breaking elongation,
%
[ I
30
40 45
* See Table 1
EXPERIMENTAL The initial diamines were obtained by the Fisher and Busch [4] method from the corresponding dinitrodiamines and methyl iodide, Subsequent reduction was carried out by the description given in a former study [5]. Bis-(3-amino-4-N-methylaminophenyl)methane is a white crystalline powder, m.p. 127-128 ° . Found, ~: C 70.04; H 7.72; N 21"90. C15H~0N4. Calculated, ~ : C 70.32; H 7.79; N 2i.81. 3.3'-Diamino-bis-~q-methylolidine, m.p. 133-134 °. Found, Yo: C 71.33; H 8.15; N 20.67. CleI-I~2N~. Calculated, ~ : C 71.07; H 8.20; N 20.72. Bis-(3-amino-4-N-methylamino-5-methylphenyl)methane, m.p. 145-146 °. Found, ~ : C 71.71; H 8.54; N 19.81. C17H~4N4. Calculated, ~ : C 71"79; H 8.48; N 19.70. The melting points of the diphenyl esters of dicarboxylic acids used were in accordance with literature data [6, 7]. The polybenzimidazoles were synthesized and their properties determined by methods described in a former report [8]. The authors are grateful to E. I. Fedin for interpreting the PNIR spectra and A. I. Mzhel'skii for carrying out the thermomechanical tests of films.
CONCLUSIONS
[ T~
(1) P o l y b e n z i m i d a z o l e s containing m e t h y l g r o u p s in t h e azole ring a n d s i m u l t a n e o u s l y in t h e azole a n d benzene rings were s y n t h e s i z e d a n d studied. (2) I t w a s p o i n t e d o u t t h a t t h e a d d i t i o n o f a l k y l g r o u p s to t h e azole ring p r o d u c e s p o l y b e n z i m i d a z o l c s of fairly high h e a t resistance a n d s a t i s f a c t o r y solubility in m a n y organic s o l w n t s a n d c a p a b l e of f o r m i n g strong elastic films. (3) P N [ R r e v e a l e d conditions for c o m p l e t e ring f o r m a t i o n d u r i n g t h e synthesis o f poly- ~q-methylbenzimidazoles. Translated by E. S E ~ R E REFERENCES
1. V. V. KORSHAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Vysokomol soyed. B9: 767, 1967 (Not translated in Polymer Sei. U.S.S.R.) 2. K. MITSUHASHI and C. S. MARVEL, J. Polymer Sci. A3: 1661, 1965 3. V. V. KORSHAK, M. M. TEPLYAKOV, R. D. FEDOROVA and Yu. Ye. DOROSHENKO, Trudy MKhTI, 57, p. 201, 1968.
New method for synthesis of cellulose chloroacetates and aminoacetates
2123
4. O. FISHER and M. BUSCH, Ber. 24; 2682, 1891 5. V. V. KORSKAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Auth. Cert. No. 218898, 1968; Byull. izobret., No. 30, 188, 1968 6. L. SCHEDER, Ber. 7: 707, 1874 7. T. M. FRUNZE, V. V. KORSHAK, A.A. IZYNEYEV and V. V. KURASHEV, Vysokomol, soyed. 7 285, 1965 (Translated in Polymer Sci. U.S.S.R. 7: 2. 313, 1965) 8. V. V. KORSHAK, M. M. TEPLYAKOV and R. D. FEDOROVA, Izv. VUZov, Khimiya i khimich, tekhnologiya 12: 193, 1969
NEW METHOD FOR THE SYNTHESIS OF CELLULOSE CHLOROACETATES AND AMINOACETATES* t A. A. KHIDOYATOVand Z. A. Rooovnv Moscow Textile Institute
(Received 21 October 1968)
CELLULOSE derivatives and esters containing amino-groups are of considerable scientific and technological interest. These materials can be easily dyed with acid dyes and can be used as anion-exchange materials [1]. Despite the extensive possibilities for improving the properties of cellulose and cellulose esters by synthesis of amino-derivatives, except for a few publications [2-5] there have been no systematic investigations carried out in this direction. Therefore developing methods for the synthesis of cellulose esters containing amino-groups and the investigation of their properties are of considerable interest. We studied the possibility of synthesizing these cellulose esters by conversion of previously synthesized cellulose ehloroacetates. Cellulose chloroacetates can be synthesized by the reaction of cellulose with monochloroacetie anhydride [6, 7] or by esterification of partially saponified acetylcellulose with monochloroacetic acid using a basic catalyst [8]. We considered it better to investigate the possibility of synthesizing these cellulose derivates by the reaction of cellulose with monochloroacetic acid chloride. According to literature data [9, 10], acetylation of cellulose by acetyl chloride with pyridine takes place via the stage of acetyl pyridinium chloride formation. Experiments show that on mixing equimolar quantities of pyridine and monochloroacetic acid chloride or valeric acid chloride a complex is formed which precipitates as a residue: ~+RCH~COCI~ N
~/
~,
RCH~COiW+C1-
where R = - - H , - - CI, -CH~CH2CH 3. * Vysokomol. soyed. A l l : No. 8, 1863-1866, 1969. ~f R. Yegorova took part in the experimental part of the study.