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Copolymerization of hydroquinone divinyl ether with methyl methacrylate
1936
A. V. KALABIlVA etal.
of 2 ml each were taken. The residue of the solution was p u t into glass ampoules, 2 ml in each. The ampoules were evacuated b y the usual freezing method (dry ice-acetone) then defrosted a n d v a c u u m sealed. The decomposition of the polycumylenethyl hydroperoxide was carried out in a thermostat.
CONCLUSIONS
By oxidizing polycumylenethyl and isopropylbenzene with oxygen in the presence of benzoyl peroxide, polycumylenethyl hydroperoxide has been produced and the kinetics of its thermal degradation in toluene have been studied with and without styrene. Translated by V. ALFORD REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
D. F. METZ and R. B. MESROBIAN, J. Polymer Sci. 16: 345, 1955 N.V. SHCHEGOLEV, Dissertation, Moscow, 1954 C. D. WAGNER, R. H. SMITH anti E. D. PETERS, Analyt. Chem. 19: 976, 1947 F. R. THOMAS, J. Amer. Chem. Soc. 77: 246, 1955 J. R. THOMAS and O. L. HARLE, J. Phys. Chem. 63: 1027, 1959 C. WALLING, Free Radicals in Solution, Izd. in. lit., !960 L. BATERMAN a n d H. HUGHES, J. Chem. Soc., 4594, 1952 V. STANNETT a n d R. B. MESROBIAN, J. Amer. Chem. Soc. 72: 4125, 1950 C, W_ALL1NG and J. W. CHANG, J. Amer. Chem. Soc. 76: 4878, 1954 N. M. EMANUEL a n d D. H. KNORRE, Course i n chemical Kinetics, 184, 1962
COPOLYMERIZATION OF HYDROQUINONE DIVINYL ETHER WITH METHYL METHACRYLATE*t A . V. K A L A B I N A , L . Y A . T S A R I K , L . A . B O D Y U K H
and YU. K. MAKSYUTIlq
I r k u t s k State University
(Received 18 November 1964)
DIVINYL ethers of bifunctional phenols (hydroquinone, pyrocateehol and resorcinol) [2] have been prepared by acetylene vinylation [1]. The literature contains descriptions of the polymerization of monovinylaryl ethers [3-5], but there is no information on any properties of the vinyl ethers of m-, o- and pdiohydroxybenzenes. These diene compounds are interesting as being new monomers capable of forming cross-linked polymers. , Vysokomol. soyed. 7: No. 10, 1758-1762, 1965. t Sixth report of the series "Investigation of the polymerization a n d copolymerization of vinylaryl ethers and their derivatives".
HQDE-MMA eopolymers
1937
In the present work the divinyl ethers of bifunctional phenols were copolymerized and studied on the example of hydroquinone divinyl ether (HQDE) and methyl methacrylate (MMA). The HQDE-MMA copolymers are of practical interest: 1) addition of HQDE to methyl methacrylate on copolymerization should raise the thermal stability of the polymethyl methacrylate, 2) HQDE and other divinyl ethers of bffunctional phenols increase the range of monomers for the synthesis o f polymers with interchain bonds. After carrying out the hom0polymerization of HQDE with the initiators azobisisobutyronitrile and benzoyl peroxide, we obtained polymers with a low yield, approx. 20%, which means that the reactivity of the divinyl ether of hydroquinone is no different f~om that of the monovinyl ethers of phenols. Since MMA is one of those monomers which can give copolymers with vinyl ethers, the system HQDE-MMA was chosen for the study of copolymerization. These monomers were copolymerized in bulk and in suspension. In the bulk reaction our aim was to discover the "cross-linking" properties of HQDE. The amount used in the original reaction mixture was varied from 1 to 20 wt. ~/o. After saponification of the ether groups, copolymers with these amounts of "cross-linking" agents will be polyelectrolytes. The results of the copolymerization are given in Table 1. TABLE 1. COPOLYMERIZATION OF H Q D E AND M M A IN BULK ( I n i t i a t o r a - - a z o b i s i s o b u t y r o n i t r i l e (1 wt, % of m o n o m e r m i x t u r e , 80 °) 50 hours) Original m o n o m e r m i x t u r e ,
wt. %
Experiment No.
HQDE
I
1
II III IV V VI
2 5 10 15 20
* The analytical figures are
MMA 99 98 95 90 85 80 the mean of two
C o n c e n t r a t i o n in copolymer,
Copolymer yield, wt.% 45"1 37"0 46"9 47"0 46 "2 34"6
%,
C 61"27 64"92 63"09 63"90 65"03 62"61
H 5"72 5"82 5"59 4"98 7"04 3"29
determinations.
The copolymerization in these experiments is confirmed by the fact that the reaction products are insoluble in the following solvents; benzene, CCI~, methanol, dich]oro~thane and dioxane; and also by the fact that the copolymers are infusible in melting point determination (in a capillary tube). Proof of the structure of the copolymers was obtained by the IR absorption spectra of samples I I I - V I (the sample number corresponds to the experiment numbers given in Table 1). Spectral analysis revealed units of both monomers
1988
A. V. I ~ n v A
~t ~.
in the copolymer. Besides this, from qualitative analysis of the intensity it can be seen that there is a gradual increase in the H Q D E unit concentration of the eopolymer as its concentration in the original reaction mixture rises. The spectrometer used was the UR-10 producted by he Karpov Physicochemical Research laboratory. The Figure shows the IR spectra of samples I I I and VI.
! f ~O#
f6#O vp~n-t
IR spectra of copolymers IiI and VL To obtain a better idea of the characteristics of H Q D E as a monomer able to act as a cross-linking agent, suspension copolymerization was carried out. The initiator was benzoyl peroxide (1% of the monomer mixture), and the stabilizers were talc and starch. Besides varying the monomer concentration, the volumetric ratio of the phases and the amounts of stabilizer were also varied during the reaction. We did this because the vinyl ethers of the aromatic series have not so far been used in this kind of suspension system. The conditions and results of the experiment axe given in Table 2. As we can see from Table 2, two stabilizers, talc and starch, are needed in order to obtain granules. The phase ratio (monomer-nonsolvent mixture) also has a big effect on the yield of the product, the best results being obtained with the ratio of 1 : 3. The suspension copolymerization of H Q D E with MMA is accompanied by emulsion copolymerization which is difficult to prevent by using electrolytes (NaC1, NaOH). The copolymer yield was found to be more dependent on the reaction conditions t h a n the amount of H Q D E in the original mixture. In bulk copolymerization t h e optimum conditions for copolymer yield were not found but, as found by carrying out this reaction in suspension, this
HQDE-MMA copolymers
1939
TABLE 2. CONDITIONSAND RESULTSOF THE SUSPENSIONCOPOLYMERIZATIONOF HQDE AND MMA HQDE : MMA Volumetric Expe;yent wt. ratio phase ratio
I$
IV
vt VI VII VIII IX X XII XIII XIV XV XVI XVII XVIII XIX XXI XXIII
10 : 90 10 : 90 5:95 10 : 90 10:90 5:95 5:95 4:95 5:95 5:95 5:95 5:95 3:97 1:99 8:92 15 : 85 5 : 95 5:95
A.inount of starch, wt.%
1:3 1:3 1:3 1:2"1 1:2"1 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:2 1:5
Amount of talc, wt.%
0"5 2 2 2 2 2 2 2 1 5 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 5 1 2 1 1 1 1 1
Copolymer yield,
%
Copolymer swelling in toluene, ~o
Flock 87.5 12.6 77.9 40.6
420 370 500
43.6 55.6 83.0 88.9 45.6 26.1
340 490 470 450
350
74.0
4OO
56.2 76.1
575
85 "2
325
56"5 41 "5 43"1
290 210
744
375
* A triple cycle did not produce granules. t NaC! added (1.5% by weight of starch).
can be as m u c h as 88~/o. I f t h e m i x i n g is uniform, granules o f t h e same size can be produced. T h e swelling o f t h e c o p o l y m e r s was d e t e r m i n e d in toluene. T h e swelling as f u n c t i o n of t h e n u m b e r o f cross-links shows some d e v i a t i o n f r o m t h a t k n o w n for cross-linked polymers. This is because H Q D E , like o t h e r v i n y l ethers, f o r m s low-molecular w e i g h t p o l y m e r s a n d copolymers. Some of t h e c o p o l y m e r s p r o d u c e d b y suspension p o l y m e r i z a t i o n were saponHQDE-MMA COPOLYMERS (80-90 °, 3 g copolymer, 0.3 mole KOH, methanol : dioxane ratio (in ml) 60 : 100)
TABLE 3. CONDITIONS AND RESULTS OF THE SAPONIFICATION OF
Experiment No.
XV XV VI VII XIX
HQDE concentration of original mixture for polymerization, % 5 5 10 10 15
Saponification time, hours
COE mg-equiv./g
2O
9"0 9"2 7"7
68
68 80 50
8"9
4-4
1940
A. V. KALABINA e t a l .
ified in order to free the carboxyl groups. This was carried out with caustic potash i n d i o x a n e a n d m e t h a n o l . T h e c o n d i t i o n s a n d r e s u l t s a r e g i v e n i n T a b l e 3. T h e t o t a l static capacity of the cations produced depends on the amount the of cross-linking agent HQDE and the extent of the saponification. Determination of the c h e m i c a l s t a b i l i t y o f t h e r e s i n w i t h 50/o H Q D E i n t h e o r i g i n a l m o n o m e r m i x t u r e u s i n g m e t h o d o f [6], s h o w e d t h i s t o b e q u i t e h i g h f o r t h e t e s t r e s i n w i t h 5 N s o l u t i o n s o f HC1, H2S04, H N 0 3 a n d K O H .
EXPERIMENTAL The initial monomers used were freshly prepared; H Q D E - - b . p . 104°/24 ram, n ~ 1"5342, d~0 1"034; M M A - - b . p . 20°/12 mm, n ~ 1"4132, d~0 0"936; azobisisobutyronitrile m.p. 102 °, benzoyl peroxide m.p. 103-5 °. Bulk polymerization was performed in ampoules which were blown through with d r y nitrogen before filling; the t o t a l monomers were 5 g. The copolymers obtained were ground, extracted in benzene until there was no qualitative reaction of the double bonds with bromine, and v a c u u m dried to constant weight. The copolymers for the I R spectra were further extracted in benzene. The suspension copolymer~zation was carried out in three-funnel flasks with a reflux condenser and an agitator. F i r s t a suspension of starch and ~alc was made. To do this a weighed a m o u n t of starch w a s dissolved in w a t e r and then the solution was added to distilled water, heated to 90 ° and held at this temperature for 90 rain with eontinous stirring. The tale was added to the starch mixture cooled to 50 ° , and then the mixture of monomers with bonzoyl peroxide was addbd. The reac%ion was carried out b y raising the temperature from 60 to 90 ° over a period of 7 hours. On completion t h e contents of the flask were cooled to room t e m p e r a t u r e and the eopolymer granules washed through a funnel with hot water a n d then cold, then with methanol, and subsequently dried in air. Saponification. The caustic potash and m e t h y l alcohol were p u t into a flask with a reflux condenser, and after the alkali h a d completely dissolved, the copolymer and dioxane were added. The reaction mixture was heated to 80-90 ° and then the contents transferred to a filter, the saponification product washed in methanol and in distiiled water, a n d dried in an desiccator. I n conclusion we would like to t a k e this o p p o r t u n i t y of thanking V. A. Sheveleva for recording the I R spectra.
CONCLUSIONS (1) Hydroquinone divinyl ether forms cross-linked copolymers with methyl methacrylate. The suspension copolymerization of hydroquinone divinyl ether with methyl methacrylate has been carried out. (2) C a r b o x y l c a t i o n i t e s h a v e b e e n s y n t h e s i z e d b y u s i n g h y d r o q u i n o n e d i v i n y l ether as the cross-linking agent. Translated by V. ALFORD
REFERENCES 1. M. F. 1952 2. A. V. 3. A. V. 1155,
SHOSTAKOVSKII, Prostye vinitov, efiry. (Vinylethers.) Izd. Akad. N a u k SSSR, 80, KALARINA a n d L. Ya. TSARIK, A u t h o r ' s statement No. 852701/23-4, 1963 KALABINA, N. A. TYUKAVKINA and V. A. KRUGLOVA, Vysokomol. soyed. 3: 1961
I R study of some cellulose graft copolymers
1941
4. A. V. KALABINA, A. Kh. FILIPPOVA ~ a/., Vysokomol. soyed. 3: 1020, 1961 5. N. A. TYUKAVK/NA, A. V. KALABINA, G. I. DERYABINA et al., Vysokomol. soyed. 6: 1573, 1964 6. K. M. SALDADZE, A. B. PASWIKOVand V. S. TITOV, Ionoobmen. vysokomol, soyed. (Ion-Exchange Macromolecular Compounds.) 99, 1960
IR STRUCTURAL STUDY OF SOME CELLULOSE GRAFT COPOLYMERS*t M. D. BALABAYEVA, YE. F. SHARKOVA, R. G. ZHBANKOV, A. D . V I R N I K a n d Z. A . ROGOVIN Moscow Textile Institute
(Received 20 November 1964)
IN [1] we described the synthesis of the graft copolymer of cellulose and polyglycidylmethacrylate (PGMA), and on its base by using the reactions of polymeranalogue conversions, we produced new graft cellulose copolymers, containing basic and acidic groups, with the following composition -cell--
CH s CH2- - C C~OCH2__CH__CH t
-
A
cell--
-
~H s CHs--C C~OCHz--CH--CH~
where A--NHs, NHsCHICHIOH, HasSOs, NaHSO3;
B-- respectively--NHs and > NH, --NI-ICHmCHIOH,---SOsNa
The composition of these graft copolymers was determined by chemical analysis. The purpose of the present work is further characterization of these graft cellulose copolymers by IR spectroscopy. The cellulose-PGMA graft copolymer was prepared with the redox system cellulosecerium ammonium nitrate. I t contained 20O//o graft PGMA and 6.6o//o epoxy groups. The Table sets out the conditions of the synthesis and the characteristics of the graft copolymers studied in the present work. * Vysokomol. soyed. 7: No. 10, 1763-1766, 1965. t 184th report of the series "Investigation of the structure and properties of cellulose and its derivatives".
A. V. KALABIlVA etal.
of 2 ml each were taken. The residue of the solution was p u t into glass ampoules, 2 ml in each. The ampoules were evacuated b y the usual freezing method (dry ice-acetone) then defrosted a n d v a c u u m sealed. The decomposition of the polycumylenethyl hydroperoxide was carried out in a thermostat.
CONCLUSIONS
By oxidizing polycumylenethyl and isopropylbenzene with oxygen in the presence of benzoyl peroxide, polycumylenethyl hydroperoxide has been produced and the kinetics of its thermal degradation in toluene have been studied with and without styrene. Translated by V. ALFORD REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
D. F. METZ and R. B. MESROBIAN, J. Polymer Sci. 16: 345, 1955 N.V. SHCHEGOLEV, Dissertation, Moscow, 1954 C. D. WAGNER, R. H. SMITH anti E. D. PETERS, Analyt. Chem. 19: 976, 1947 F. R. THOMAS, J. Amer. Chem. Soc. 77: 246, 1955 J. R. THOMAS and O. L. HARLE, J. Phys. Chem. 63: 1027, 1959 C. WALLING, Free Radicals in Solution, Izd. in. lit., !960 L. BATERMAN a n d H. HUGHES, J. Chem. Soc., 4594, 1952 V. STANNETT a n d R. B. MESROBIAN, J. Amer. Chem. Soc. 72: 4125, 1950 C, W_ALL1NG and J. W. CHANG, J. Amer. Chem. Soc. 76: 4878, 1954 N. M. EMANUEL a n d D. H. KNORRE, Course i n chemical Kinetics, 184, 1962
COPOLYMERIZATION OF HYDROQUINONE DIVINYL ETHER WITH METHYL METHACRYLATE*t A . V. K A L A B I N A , L . Y A . T S A R I K , L . A . B O D Y U K H
and YU. K. MAKSYUTIlq
I r k u t s k State University
(Received 18 November 1964)
DIVINYL ethers of bifunctional phenols (hydroquinone, pyrocateehol and resorcinol) [2] have been prepared by acetylene vinylation [1]. The literature contains descriptions of the polymerization of monovinylaryl ethers [3-5], but there is no information on any properties of the vinyl ethers of m-, o- and pdiohydroxybenzenes. These diene compounds are interesting as being new monomers capable of forming cross-linked polymers. , Vysokomol. soyed. 7: No. 10, 1758-1762, 1965. t Sixth report of the series "Investigation of the polymerization a n d copolymerization of vinylaryl ethers and their derivatives".
HQDE-MMA eopolymers
1937
In the present work the divinyl ethers of bifunctional phenols were copolymerized and studied on the example of hydroquinone divinyl ether (HQDE) and methyl methacrylate (MMA). The HQDE-MMA copolymers are of practical interest: 1) addition of HQDE to methyl methacrylate on copolymerization should raise the thermal stability of the polymethyl methacrylate, 2) HQDE and other divinyl ethers of bffunctional phenols increase the range of monomers for the synthesis o f polymers with interchain bonds. After carrying out the hom0polymerization of HQDE with the initiators azobisisobutyronitrile and benzoyl peroxide, we obtained polymers with a low yield, approx. 20%, which means that the reactivity of the divinyl ether of hydroquinone is no different f~om that of the monovinyl ethers of phenols. Since MMA is one of those monomers which can give copolymers with vinyl ethers, the system HQDE-MMA was chosen for the study of copolymerization. These monomers were copolymerized in bulk and in suspension. In the bulk reaction our aim was to discover the "cross-linking" properties of HQDE. The amount used in the original reaction mixture was varied from 1 to 20 wt. ~/o. After saponification of the ether groups, copolymers with these amounts of "cross-linking" agents will be polyelectrolytes. The results of the copolymerization are given in Table 1. TABLE 1. COPOLYMERIZATION OF H Q D E AND M M A IN BULK ( I n i t i a t o r a - - a z o b i s i s o b u t y r o n i t r i l e (1 wt, % of m o n o m e r m i x t u r e , 80 °) 50 hours) Original m o n o m e r m i x t u r e ,
wt. %
Experiment No.
HQDE
I
1
II III IV V VI
2 5 10 15 20
* The analytical figures are
MMA 99 98 95 90 85 80 the mean of two
C o n c e n t r a t i o n in copolymer,
Copolymer yield, wt.% 45"1 37"0 46"9 47"0 46 "2 34"6
%,
C 61"27 64"92 63"09 63"90 65"03 62"61
H 5"72 5"82 5"59 4"98 7"04 3"29
determinations.
The copolymerization in these experiments is confirmed by the fact that the reaction products are insoluble in the following solvents; benzene, CCI~, methanol, dich]oro~thane and dioxane; and also by the fact that the copolymers are infusible in melting point determination (in a capillary tube). Proof of the structure of the copolymers was obtained by the IR absorption spectra of samples I I I - V I (the sample number corresponds to the experiment numbers given in Table 1). Spectral analysis revealed units of both monomers
1988
A. V. I ~ n v A
~t ~.
in the copolymer. Besides this, from qualitative analysis of the intensity it can be seen that there is a gradual increase in the H Q D E unit concentration of the eopolymer as its concentration in the original reaction mixture rises. The spectrometer used was the UR-10 producted by he Karpov Physicochemical Research laboratory. The Figure shows the IR spectra of samples I I I and VI.
! f ~O#
f6#O vp~n-t
IR spectra of copolymers IiI and VL To obtain a better idea of the characteristics of H Q D E as a monomer able to act as a cross-linking agent, suspension copolymerization was carried out. The initiator was benzoyl peroxide (1% of the monomer mixture), and the stabilizers were talc and starch. Besides varying the monomer concentration, the volumetric ratio of the phases and the amounts of stabilizer were also varied during the reaction. We did this because the vinyl ethers of the aromatic series have not so far been used in this kind of suspension system. The conditions and results of the experiment axe given in Table 2. As we can see from Table 2, two stabilizers, talc and starch, are needed in order to obtain granules. The phase ratio (monomer-nonsolvent mixture) also has a big effect on the yield of the product, the best results being obtained with the ratio of 1 : 3. The suspension copolymerization of H Q D E with MMA is accompanied by emulsion copolymerization which is difficult to prevent by using electrolytes (NaC1, NaOH). The copolymer yield was found to be more dependent on the reaction conditions t h a n the amount of H Q D E in the original mixture. In bulk copolymerization t h e optimum conditions for copolymer yield were not found but, as found by carrying out this reaction in suspension, this
HQDE-MMA copolymers
1939
TABLE 2. CONDITIONSAND RESULTSOF THE SUSPENSIONCOPOLYMERIZATIONOF HQDE AND MMA HQDE : MMA Volumetric Expe;yent wt. ratio phase ratio
I$
IV
vt VI VII VIII IX X XII XIII XIV XV XVI XVII XVIII XIX XXI XXIII
10 : 90 10 : 90 5:95 10 : 90 10:90 5:95 5:95 4:95 5:95 5:95 5:95 5:95 3:97 1:99 8:92 15 : 85 5 : 95 5:95
A.inount of starch, wt.%
1:3 1:3 1:3 1:2"1 1:2"1 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:3 1:2 1:5
Amount of talc, wt.%
0"5 2 2 2 2 2 2 2 1 5 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 5 1 2 1 1 1 1 1
Copolymer yield,
%
Copolymer swelling in toluene, ~o
Flock 87.5 12.6 77.9 40.6
420 370 500
43.6 55.6 83.0 88.9 45.6 26.1
340 490 470 450
350
74.0
4OO
56.2 76.1
575
85 "2
325
56"5 41 "5 43"1
290 210
744
375
* A triple cycle did not produce granules. t NaC! added (1.5% by weight of starch).
can be as m u c h as 88~/o. I f t h e m i x i n g is uniform, granules o f t h e same size can be produced. T h e swelling o f t h e c o p o l y m e r s was d e t e r m i n e d in toluene. T h e swelling as f u n c t i o n of t h e n u m b e r o f cross-links shows some d e v i a t i o n f r o m t h a t k n o w n for cross-linked polymers. This is because H Q D E , like o t h e r v i n y l ethers, f o r m s low-molecular w e i g h t p o l y m e r s a n d copolymers. Some of t h e c o p o l y m e r s p r o d u c e d b y suspension p o l y m e r i z a t i o n were saponHQDE-MMA COPOLYMERS (80-90 °, 3 g copolymer, 0.3 mole KOH, methanol : dioxane ratio (in ml) 60 : 100)
TABLE 3. CONDITIONS AND RESULTS OF THE SAPONIFICATION OF
Experiment No.
XV XV VI VII XIX
HQDE concentration of original mixture for polymerization, % 5 5 10 10 15
Saponification time, hours
COE mg-equiv./g
2O
9"0 9"2 7"7
68
68 80 50
8"9
4-4
1940
A. V. KALABINA e t a l .
ified in order to free the carboxyl groups. This was carried out with caustic potash i n d i o x a n e a n d m e t h a n o l . T h e c o n d i t i o n s a n d r e s u l t s a r e g i v e n i n T a b l e 3. T h e t o t a l static capacity of the cations produced depends on the amount the of cross-linking agent HQDE and the extent of the saponification. Determination of the c h e m i c a l s t a b i l i t y o f t h e r e s i n w i t h 50/o H Q D E i n t h e o r i g i n a l m o n o m e r m i x t u r e u s i n g m e t h o d o f [6], s h o w e d t h i s t o b e q u i t e h i g h f o r t h e t e s t r e s i n w i t h 5 N s o l u t i o n s o f HC1, H2S04, H N 0 3 a n d K O H .
EXPERIMENTAL The initial monomers used were freshly prepared; H Q D E - - b . p . 104°/24 ram, n ~ 1"5342, d~0 1"034; M M A - - b . p . 20°/12 mm, n ~ 1"4132, d~0 0"936; azobisisobutyronitrile m.p. 102 °, benzoyl peroxide m.p. 103-5 °. Bulk polymerization was performed in ampoules which were blown through with d r y nitrogen before filling; the t o t a l monomers were 5 g. The copolymers obtained were ground, extracted in benzene until there was no qualitative reaction of the double bonds with bromine, and v a c u u m dried to constant weight. The copolymers for the I R spectra were further extracted in benzene. The suspension copolymer~zation was carried out in three-funnel flasks with a reflux condenser and an agitator. F i r s t a suspension of starch and ~alc was made. To do this a weighed a m o u n t of starch w a s dissolved in w a t e r and then the solution was added to distilled water, heated to 90 ° and held at this temperature for 90 rain with eontinous stirring. The tale was added to the starch mixture cooled to 50 ° , and then the mixture of monomers with bonzoyl peroxide was addbd. The reac%ion was carried out b y raising the temperature from 60 to 90 ° over a period of 7 hours. On completion t h e contents of the flask were cooled to room t e m p e r a t u r e and the eopolymer granules washed through a funnel with hot water a n d then cold, then with methanol, and subsequently dried in air. Saponification. The caustic potash and m e t h y l alcohol were p u t into a flask with a reflux condenser, and after the alkali h a d completely dissolved, the copolymer and dioxane were added. The reaction mixture was heated to 80-90 ° and then the contents transferred to a filter, the saponification product washed in methanol and in distiiled water, a n d dried in an desiccator. I n conclusion we would like to t a k e this o p p o r t u n i t y of thanking V. A. Sheveleva for recording the I R spectra.
CONCLUSIONS (1) Hydroquinone divinyl ether forms cross-linked copolymers with methyl methacrylate. The suspension copolymerization of hydroquinone divinyl ether with methyl methacrylate has been carried out. (2) C a r b o x y l c a t i o n i t e s h a v e b e e n s y n t h e s i z e d b y u s i n g h y d r o q u i n o n e d i v i n y l ether as the cross-linking agent. Translated by V. ALFORD
REFERENCES 1. M. F. 1952 2. A. V. 3. A. V. 1155,
SHOSTAKOVSKII, Prostye vinitov, efiry. (Vinylethers.) Izd. Akad. N a u k SSSR, 80, KALARINA a n d L. Ya. TSARIK, A u t h o r ' s statement No. 852701/23-4, 1963 KALABINA, N. A. TYUKAVKINA and V. A. KRUGLOVA, Vysokomol. soyed. 3: 1961
I R study of some cellulose graft copolymers
1941
4. A. V. KALABINA, A. Kh. FILIPPOVA ~ a/., Vysokomol. soyed. 3: 1020, 1961 5. N. A. TYUKAVK/NA, A. V. KALABINA, G. I. DERYABINA et al., Vysokomol. soyed. 6: 1573, 1964 6. K. M. SALDADZE, A. B. PASWIKOVand V. S. TITOV, Ionoobmen. vysokomol, soyed. (Ion-Exchange Macromolecular Compounds.) 99, 1960
IR STRUCTURAL STUDY OF SOME CELLULOSE GRAFT COPOLYMERS*t M. D. BALABAYEVA, YE. F. SHARKOVA, R. G. ZHBANKOV, A. D . V I R N I K a n d Z. A . ROGOVIN Moscow Textile Institute
(Received 20 November 1964)
IN [1] we described the synthesis of the graft copolymer of cellulose and polyglycidylmethacrylate (PGMA), and on its base by using the reactions of polymeranalogue conversions, we produced new graft cellulose copolymers, containing basic and acidic groups, with the following composition -cell--
CH s CH2- - C C~OCH2__CH__CH t
-
A
cell--
-
~H s CHs--C C~OCHz--CH--CH~
where A--NHs, NHsCHICHIOH, HasSOs, NaHSO3;
B-- respectively--NHs and > NH, --NI-ICHmCHIOH,---SOsNa
The composition of these graft copolymers was determined by chemical analysis. The purpose of the present work is further characterization of these graft cellulose copolymers by IR spectroscopy. The cellulose-PGMA graft copolymer was prepared with the redox system cellulosecerium ammonium nitrate. I t contained 20O//o graft PGMA and 6.6o//o epoxy groups. The Table sets out the conditions of the synthesis and the characteristics of the graft copolymers studied in the present work. * Vysokomol. soyed. 7: No. 10, 1763-1766, 1965. t 184th report of the series "Investigation of the structure and properties of cellulose and its derivatives".