- Email: [email protected]
Role of the complex of p-benzoquinone and styrene in their cationic copolymerization
1514
A. Yu. NAGIYEV et al.
59. V. A. BERSHTEIN, Yu. A. YEMEL'YANOV and V. A. STEPANOV, Vysokomol. soyed. A26: 2272, 1984 (Translated in Polymer Sci. U.S.S.R. 26: 11, 2539, 1984) 60. G. K. MOSCICKI, G. WILLIAMS and S. M. AHARONI, Polymer 22: 1361, 1981 61. G. P. JOHARI and M. GOLDSTEIN, J. Chem. Phys. 53: 2372, 1970 62. A. L. KOVARSKII, S. A. MANSIMOV and A. L. BUCHACHENKO, Dokl. Akad. Nauk SSSR 291: No. 6, 1986
Polymer Science U.S.S.R. Vol. 28, No. 7, pp. 1514-1518, 1986 Printed in Poland
0032-3950/86 $10.00+.00 © 1987 PergamonJournals Ltd.
ROLE OF THE COMPLEX OF p-BENZOQUINONE AND STYRENE IN THEIR CATIONIC COPOLYMERIZATION* A. Y u . NAGIYEV, A . V. R~GIMOV a n d B. I. LIOGON'KII Institute of Organochlorine Synthesis, Az.S.S.R. Academy of Sciences Institute of Chemical Physics, U.S.S.R. Academy of Sciences (Received 7 September 1984) The formation of donor-acceptor complexes between styrene and p-benzoquinone has been investigated. "Ihe complexing constant amounting to 0.11 l./mole has been determined. It has been established that the complex of p-benzoquinone and styrene exerts, a positive influence on the rate of polymerization of styrene and copolymerization of styrene with p-benzoquinone and shortens their induction period. From the results obtained and the kinetics of the process and also the structure in the end products, the authors propose a mechanism for the copolymerizaticn cf sty~ne t~d p-bcnzcquincne. It is shown that the complexes of p-benzoquinone and styrene regulate the comrc~ition ,~nd structure of the copolymers obtained. A link between the concentration of this complex, the MD and M of the products formed has been established which is explained by the participation of the complex in the act of chain transfer. Trn~ c o m p l e x i n g p r o p e r t i e s c h a r a c t e r i s t i c o f the quinones have been quite widely studied [1]. H o w e v e r , complexes w i t h strong d o n o r s (amines) have in the m a i n been investigated. T h e role in cationic p o l y m e r i z a t i o n processes o f w e a k q u i n o n e c o m p l e x e s w i t h u n s a t u r a t e d c o m p o u n d s c a p a b l e o f p o l y m e r i z a t i o n has n o t been s t u d i e d b u t the c o c a t a l y t i c effect o f the quinones in p o l y m e r i z a t i o n o f the olefines in presence o f d i a l k y t a l u m i n i u m halides is k n o w n [2]. I n [3] it is shown that the f o r m a t i o n o f the c o m p l e x o f p - b e n z o q u i n o n e (BQ) with water B Q ' H 2 0 p r o m o t e s p o l y m e r i z a t i o n o f B Q in a b sence o f a n i n i t i a t o r at low t e m p e r a t u r e s in a q u e o u s solution. This fact also p r e d e t e r m i n e s the desirability o f investigating b o t h the role o f w e a k BQ a n d styrene c o m p l e x e s * Vysokomol. soyed. A28: No. 7, 1361-1364, 1986.
Role of complex of p-benzoquinone and styrene in their cationic copolymerization 1515 in the processes of their polymerization and copolymerization on cationic initiation [4] and the possibility of the targetted influence on the rate of these reactions and the molecular mass characteristics of the copolymers. The present work is concerned with complexing between BQ and styrene and its influence on the course and products of the cationic polymerization of styrene and its copolymerization with BQ. Complexing between BQ and styrene was by the PMR mgthod for a 10}/osolution in deuterobenzene (internal standard HMDS) with the Tcsla BS-487 B instrument with a working frequency 80 Hz at room temperature. The kinetics of the cationic polymerization of styrene (0.6374 mole/1.) in presence of BQ and boron trifluoride etherate (0.632x10 -2 mole/l.) in benzene was studied by dilatometry at 10-a mm Hg as in reference [5]. Before use p-benzoquinone was twice sublimated, styrene was treated with aqueous alkaline solution, washed with water, dried ov:r CaC12 and distilled over BaO. The physical chemical constants of BQ and styr~::~e co-r,-sponded to those in the literature. Earlier, Tudos postulated the possibility of formation of a donor-aceeptor complex between BQ and styrene although he did not confirm it experimentally [6]. The results of our investigations of a mixture of BQ and styrene in deuterobenzene by P M R spectroscopy revealed (Fig. 1, Table) an appreciable shift in the signal of the protons of the multiple bonds of BQ (3=6.66 ppm) forming part of the complex to a strong field (An=0-06 ppm) and of styrene (6=5.60 ppm) to a weak field (A6=0.03 ppm). The signal of the CH3 groups of pure styrene appears in the form of a triplet with the constants of spin-spin interaction/1 = 18 and 12= 11 Hz. In the spectrum of styrene complexed with BQ their value falls to 16.0 and 9.5 Hz respectively. Thus, the changes found in the chemical shifts and the values of the constants of the spin-spin interaction of BQ and styrene protons point to the formation of donoracceptor complexes in the mixture of monomers studied (Table). On the basis of the chemical shifts observed in the symmetrical protons of the double BQ bond from the graphic dependence of llAa on [Ml] where M, is styrene (Fig. 2) using the Benesi-Hildebrand and Katelaar equation [7] 1
R E S U L T S OF
PMR
l
1
SPECTROSCOPY FOR DETERMINING THE COMPLEX1NG CONSTANTS OF STYRENE
(M~)
AND BQ
[BQ] 0-1 0.1 0.1 0.1 0"1 0.1
t [Styrene] mok/l. 8 6 4 2 1 0"1
& . = c u of quinone, ppm 6"18 6"25 6"35 6"48 6"57 6"66
Ad, ppm
I/A& (ppm)- 1
0"48 0-38 0.31 0.18 0.09 0.06
2.10 2'64 3.23 5"55 11"60 16"60
1/[M1]o,
(mole/I.)- t 0"125 0"167 0"25 0.50 1-0
A. Yu. NAGIYEVet al.
1516
where AO is the difference in the chemical shifts of the BQ protons, ppm; A6 (ppm) is the difference in the chemical shifts of the protons of BQ forming part of the complex we found the constant of complexing for the pair styrene ... BQ which was K=O.11 l./mole.
b_
J~:
J•J
2
J 7
3 I __ ~ ~?,om
I G
/J
I0
/°/ 1 0.2
I I 0.6 t-00 I/[M~], (mo/~/,'.y'
FIo. 1
FIG. 2
FIG. 1. PMR spectra in C6D6 of 10~o solutions of styrene (1), BQ (2) and an equimolar mixture of BQ and styrene (3). FIG. 2. Determination of the complexing constants for the monomer pair styrene and BQ.
Fn! , re'o/. ~,:;~7/,oft
o! 08
O'q
'
O
I
o.q Fio. 3
I
O.S
2a
z9
:5 v~, c.un:,~ Fro. 4
FIG. 3. Monomer composition of the copolymer of styrene and BQ according to elemental (1) and hydroxyl (2) analysis. FIO. 4. Effect of addition of the BQ-styrene complex on the MD of ollgostyrene. [Ml]o =0-70; [BFa'O(C2H~)2]o=0"008 mole/l.; [BQ]=0 (1), 2.0 (2) and 10 (3) grav.~ 20"C.
Role of complex of p-benzoquinone and styrene in their cationic copolymerization 1517 Despite the low concentration of the complex of BQ and styrene and the weak acceptor properties of BQ itself, this complex plays the main role in the process of cationic polymerization of styrene [5] in presence of boron trifluoride etherate. It was established, for example, that in presence of 2 mole. O//oof the BQ.styrene complex the rate of polymerization of styrene at 30°C rises from 2.42 × 10-5 to 11.53 × l0 -s mole/l..sec and the induction period shortens from 22 to 4 rain. The determinant role of the BQ.styrene complex in the acceleration of cationic polymerization of styrene is confirmed by the dependence of these phenomena on the order of the shift of BQ and initiator: acceleration of polymerization of styrene is observed only on addition of initiator to the mixture of BQ and styrene. Thanks to the formation of the molecular complex of BQ and styrene on cationic copolymerization a tendency for alternating copolymers to form is observed (Fig. 3). A similar tendency was found by [toh and [watsuki [8, 9] in study of the polymerization of the complex dichlorodicyano-p-benzoquinone with styrene. Evidently the redistribution of electron density in the BQ-styrene complex favours the formation of copolymerization products consisting of hydroquinone and styrene units. Were this not the case, one would have to expect the tormation of copolymers with a polyether structure [4]. The complex of styrene and BQ has a determinant influence not only on the mechanism of the process and the structure of the copolymers but also in their molecular masses and MD. Thus, cationic polymerization of styrene in presence of even small amounts (2 mole. %) of the BQ.styrene complex appreciably changes the general form of the gel chromatograms of the polymerization products (Fig. 4) and shifts the maximum in the MD curves to low molecular masses and reduces ASrn and )~tv from 1910 and 6700 to 1460 and 3370 respectively. In these changes the most important factor is the sharp fall in the polydispersity coefficient of the polymerization products (from 3.51 to 2-30) which is of practical importance in regulating the MD and synthesis of reactive oligomers with set molecular masses and polydispersity. With increase in the content if the BQ.styrene complex to 10 mole % the polydispersity of the polymers falls to 1.20. Evidently, these findings are due to the participation of the BQ.styrene complex in the regulation of M and the polydispersity of the polymers [10]. The authors wish to thank A. I. Kuzayev for consultation in study of the MD of the copolymers. Translated by A. CROZY REFERENCES
1. T. NOGAMI, K. YOSHIHARA, H. HOSOYA and S. NAGAKURA, J. Phys. Chem. 73: 2670, 1969 2. S. CESCA, A. PRIOLA, G. FERRARIS, C. BUSSETTO and M. BRUZZONE, J. Polymer Sci. 14: 159, 1976 3. A. V. RAGIMOV, F. T, BEKTASHI and B. I. LIOGON'KII, Vysokomol. soyed. A17: 2753, 1975 (Translated in Polymer Sci. U.S.S.R. 17: 12, 3164, 1975) 4. A. V. RAGIMOV, A. Yu. NAGIEV, B. I. LIOGONKY and A. A. BERLIN, J. Polymer Sci. Polymer Chem. Ed. 18: 713, 1980
Yu. I. MATVEYEVand A. A. ASKADSKII
1518
5. A. V. RAGIMOV, A. Yu. NAGIYEV, R. A. KURBANOVA, B. I. LIOGON'KII and A. A. BERLIN, Vysokomol. soyed. A21: 382, 1979 (Translated in Polymer Sci. U.S.S.R. 21: 2, 418, 1979) 6. F. TUDOS, Acta Chem. Scand. 44: 409, 1966 7. U. A. BENESI and J. U. HILDEBRAND, J. Amer. Chem. Soc. 71: 2703, 1049; J. A. A. KETELAAR, Rec. trav. chem. 71: 1104, 1952 8. T. KOKUBO, S. IWATSUKI and Y. YAMASHITO, Macromolecules 1: 482, 1968 9. S. IWATSUKI and A. ITOH, J. Polymer Sci. Polymer Chem. Ed. 18: 2971, 1980 10. A. V. RAGIMOV, A. Yu. NAGIEV, A. I. KUZAEV and B. I. LIOGONKY, Polymer 23: 1387, 1982
Polymer ScienceU.S.S.R.Vol. 28, No. 7, pp. 1518-1527, 1986 ]Printed in Poland
0032-3950/86 $10.00+.00 © 1987PergamonJournals Ltd.
FORMATION OF SUPRAMOLECULAR STRUCTURES IN AMORPHOUS POLYMERS* Yu. I. MATVEYEV a n d A. A . ASKADSKII Kuibyshev Engineering-Construction Institute, Moscow (Received 9 September 1984) A scheme of the formation of the elements of the supramolecular structure of polymers on the basis of the Lifshits theory of the "coil-globule" transition is proposed and analysed. The scheme helps to explain a number of phenomena observed experimentally during the formation of polymer bodies from solutions (the influence of the quality of the solvent on the properties, plasticization and antiplasticization, etc.) and to predict ways of obtaining polymer bodies with the desired structure and properties. THE e x p e r i m e n t a l m a t e r i a l n o w to h a n d a n d a l s o the t h e o r e t i c a l investigations o f p o l y m e r s help to m a p out a scheme o f the f o r m a t i o n o f s u p e r m o l e c u l a r structures (s.m.s.) a n d f r o m this scheme a t t e m p t to establish the link between the c h e m i c a l struc, ture o f the p o l y m e r , its s.m.s, a n d p h y s i c a l p r o p e r t i e s . T h e p r o b l e m o f the s.m.s.s a n d t h e i r forms was first f o r m u l a t e d in [1]. V a r i o u s s.m.s, m o d e l s t h e n a p p e a r e d [2, 3] h e l p i n g to explain a n u m b e r o f p r o p e r t i e s o f a m o r p h o u s p o l y m e r s in solutions, the m e l t a n d solid state. Simultaneous w i t h m o d e l concepts n u m e r o u s e x p e r i m e n t s were c a r r i e d o u t to detect the s.m.s, b y various m e t h o d s , the m o s t w i d e l y a d o p t e d being t h a t o f e l e c t r o n microscopy. T h e m o s t c h a r a c t e r i s t i c picture o b s e r v e d in a m o r p h o u s p o l y m e r s is t h a t o f globules the size o f w h i c h c o r r e s p o n d s to aggregates o f tens a n d h u n d r e d s of macromolecules. .Vysokomol. soyed. A28: No. 7, 1365-1372, 1986.
A. Yu. NAGIYEV et al.
59. V. A. BERSHTEIN, Yu. A. YEMEL'YANOV and V. A. STEPANOV, Vysokomol. soyed. A26: 2272, 1984 (Translated in Polymer Sci. U.S.S.R. 26: 11, 2539, 1984) 60. G. K. MOSCICKI, G. WILLIAMS and S. M. AHARONI, Polymer 22: 1361, 1981 61. G. P. JOHARI and M. GOLDSTEIN, J. Chem. Phys. 53: 2372, 1970 62. A. L. KOVARSKII, S. A. MANSIMOV and A. L. BUCHACHENKO, Dokl. Akad. Nauk SSSR 291: No. 6, 1986
Polymer Science U.S.S.R. Vol. 28, No. 7, pp. 1514-1518, 1986 Printed in Poland
0032-3950/86 $10.00+.00 © 1987 PergamonJournals Ltd.
ROLE OF THE COMPLEX OF p-BENZOQUINONE AND STYRENE IN THEIR CATIONIC COPOLYMERIZATION* A. Y u . NAGIYEV, A . V. R~GIMOV a n d B. I. LIOGON'KII Institute of Organochlorine Synthesis, Az.S.S.R. Academy of Sciences Institute of Chemical Physics, U.S.S.R. Academy of Sciences (Received 7 September 1984) The formation of donor-acceptor complexes between styrene and p-benzoquinone has been investigated. "Ihe complexing constant amounting to 0.11 l./mole has been determined. It has been established that the complex of p-benzoquinone and styrene exerts, a positive influence on the rate of polymerization of styrene and copolymerization of styrene with p-benzoquinone and shortens their induction period. From the results obtained and the kinetics of the process and also the structure in the end products, the authors propose a mechanism for the copolymerizaticn cf sty~ne t~d p-bcnzcquincne. It is shown that the complexes of p-benzoquinone and styrene regulate the comrc~ition ,~nd structure of the copolymers obtained. A link between the concentration of this complex, the MD and M of the products formed has been established which is explained by the participation of the complex in the act of chain transfer. Trn~ c o m p l e x i n g p r o p e r t i e s c h a r a c t e r i s t i c o f the quinones have been quite widely studied [1]. H o w e v e r , complexes w i t h strong d o n o r s (amines) have in the m a i n been investigated. T h e role in cationic p o l y m e r i z a t i o n processes o f w e a k q u i n o n e c o m p l e x e s w i t h u n s a t u r a t e d c o m p o u n d s c a p a b l e o f p o l y m e r i z a t i o n has n o t been s t u d i e d b u t the c o c a t a l y t i c effect o f the quinones in p o l y m e r i z a t i o n o f the olefines in presence o f d i a l k y t a l u m i n i u m halides is k n o w n [2]. I n [3] it is shown that the f o r m a t i o n o f the c o m p l e x o f p - b e n z o q u i n o n e (BQ) with water B Q ' H 2 0 p r o m o t e s p o l y m e r i z a t i o n o f B Q in a b sence o f a n i n i t i a t o r at low t e m p e r a t u r e s in a q u e o u s solution. This fact also p r e d e t e r m i n e s the desirability o f investigating b o t h the role o f w e a k BQ a n d styrene c o m p l e x e s * Vysokomol. soyed. A28: No. 7, 1361-1364, 1986.
Role of complex of p-benzoquinone and styrene in their cationic copolymerization 1515 in the processes of their polymerization and copolymerization on cationic initiation [4] and the possibility of the targetted influence on the rate of these reactions and the molecular mass characteristics of the copolymers. The present work is concerned with complexing between BQ and styrene and its influence on the course and products of the cationic polymerization of styrene and its copolymerization with BQ. Complexing between BQ and styrene was by the PMR mgthod for a 10}/osolution in deuterobenzene (internal standard HMDS) with the Tcsla BS-487 B instrument with a working frequency 80 Hz at room temperature. The kinetics of the cationic polymerization of styrene (0.6374 mole/1.) in presence of BQ and boron trifluoride etherate (0.632x10 -2 mole/l.) in benzene was studied by dilatometry at 10-a mm Hg as in reference [5]. Before use p-benzoquinone was twice sublimated, styrene was treated with aqueous alkaline solution, washed with water, dried ov:r CaC12 and distilled over BaO. The physical chemical constants of BQ and styr~::~e co-r,-sponded to those in the literature. Earlier, Tudos postulated the possibility of formation of a donor-aceeptor complex between BQ and styrene although he did not confirm it experimentally [6]. The results of our investigations of a mixture of BQ and styrene in deuterobenzene by P M R spectroscopy revealed (Fig. 1, Table) an appreciable shift in the signal of the protons of the multiple bonds of BQ (3=6.66 ppm) forming part of the complex to a strong field (An=0-06 ppm) and of styrene (6=5.60 ppm) to a weak field (A6=0.03 ppm). The signal of the CH3 groups of pure styrene appears in the form of a triplet with the constants of spin-spin interaction/1 = 18 and 12= 11 Hz. In the spectrum of styrene complexed with BQ their value falls to 16.0 and 9.5 Hz respectively. Thus, the changes found in the chemical shifts and the values of the constants of the spin-spin interaction of BQ and styrene protons point to the formation of donoracceptor complexes in the mixture of monomers studied (Table). On the basis of the chemical shifts observed in the symmetrical protons of the double BQ bond from the graphic dependence of llAa on [Ml] where M, is styrene (Fig. 2) using the Benesi-Hildebrand and Katelaar equation [7] 1
R E S U L T S OF
PMR
l
1
SPECTROSCOPY FOR DETERMINING THE COMPLEX1NG CONSTANTS OF STYRENE
(M~)
AND BQ
[BQ] 0-1 0.1 0.1 0.1 0"1 0.1
t [Styrene] mok/l. 8 6 4 2 1 0"1
& . = c u of quinone, ppm 6"18 6"25 6"35 6"48 6"57 6"66
Ad, ppm
I/A& (ppm)- 1
0"48 0-38 0.31 0.18 0.09 0.06
2.10 2'64 3.23 5"55 11"60 16"60
1/[M1]o,
(mole/I.)- t 0"125 0"167 0"25 0.50 1-0
A. Yu. NAGIYEVet al.
1516
where AO is the difference in the chemical shifts of the BQ protons, ppm; A6 (ppm) is the difference in the chemical shifts of the protons of BQ forming part of the complex we found the constant of complexing for the pair styrene ... BQ which was K=O.11 l./mole.
b_
J~:
J•J
2
J 7
3 I __ ~ ~?,om
I G
/J
I0
/°/ 1 0.2
I I 0.6 t-00 I/[M~], (mo/~/,'.y'
FIo. 1
FIG. 2
FIG. 1. PMR spectra in C6D6 of 10~o solutions of styrene (1), BQ (2) and an equimolar mixture of BQ and styrene (3). FIG. 2. Determination of the complexing constants for the monomer pair styrene and BQ.
Fn! , re'o/. ~,:;~7/,oft
o! 08
O'q
'
O
I
o.q Fio. 3
I
O.S
2a
z9
:5 v~, c.un:,~ Fro. 4
FIG. 3. Monomer composition of the copolymer of styrene and BQ according to elemental (1) and hydroxyl (2) analysis. FIO. 4. Effect of addition of the BQ-styrene complex on the MD of ollgostyrene. [Ml]o =0-70; [BFa'O(C2H~)2]o=0"008 mole/l.; [BQ]=0 (1), 2.0 (2) and 10 (3) grav.~ 20"C.
Role of complex of p-benzoquinone and styrene in their cationic copolymerization 1517 Despite the low concentration of the complex of BQ and styrene and the weak acceptor properties of BQ itself, this complex plays the main role in the process of cationic polymerization of styrene [5] in presence of boron trifluoride etherate. It was established, for example, that in presence of 2 mole. O//oof the BQ.styrene complex the rate of polymerization of styrene at 30°C rises from 2.42 × 10-5 to 11.53 × l0 -s mole/l..sec and the induction period shortens from 22 to 4 rain. The determinant role of the BQ.styrene complex in the acceleration of cationic polymerization of styrene is confirmed by the dependence of these phenomena on the order of the shift of BQ and initiator: acceleration of polymerization of styrene is observed only on addition of initiator to the mixture of BQ and styrene. Thanks to the formation of the molecular complex of BQ and styrene on cationic copolymerization a tendency for alternating copolymers to form is observed (Fig. 3). A similar tendency was found by [toh and [watsuki [8, 9] in study of the polymerization of the complex dichlorodicyano-p-benzoquinone with styrene. Evidently the redistribution of electron density in the BQ-styrene complex favours the formation of copolymerization products consisting of hydroquinone and styrene units. Were this not the case, one would have to expect the tormation of copolymers with a polyether structure [4]. The complex of styrene and BQ has a determinant influence not only on the mechanism of the process and the structure of the copolymers but also in their molecular masses and MD. Thus, cationic polymerization of styrene in presence of even small amounts (2 mole. %) of the BQ.styrene complex appreciably changes the general form of the gel chromatograms of the polymerization products (Fig. 4) and shifts the maximum in the MD curves to low molecular masses and reduces ASrn and )~tv from 1910 and 6700 to 1460 and 3370 respectively. In these changes the most important factor is the sharp fall in the polydispersity coefficient of the polymerization products (from 3.51 to 2-30) which is of practical importance in regulating the MD and synthesis of reactive oligomers with set molecular masses and polydispersity. With increase in the content if the BQ.styrene complex to 10 mole % the polydispersity of the polymers falls to 1.20. Evidently, these findings are due to the participation of the BQ.styrene complex in the regulation of M and the polydispersity of the polymers [10]. The authors wish to thank A. I. Kuzayev for consultation in study of the MD of the copolymers. Translated by A. CROZY REFERENCES
1. T. NOGAMI, K. YOSHIHARA, H. HOSOYA and S. NAGAKURA, J. Phys. Chem. 73: 2670, 1969 2. S. CESCA, A. PRIOLA, G. FERRARIS, C. BUSSETTO and M. BRUZZONE, J. Polymer Sci. 14: 159, 1976 3. A. V. RAGIMOV, F. T, BEKTASHI and B. I. LIOGON'KII, Vysokomol. soyed. A17: 2753, 1975 (Translated in Polymer Sci. U.S.S.R. 17: 12, 3164, 1975) 4. A. V. RAGIMOV, A. Yu. NAGIEV, B. I. LIOGONKY and A. A. BERLIN, J. Polymer Sci. Polymer Chem. Ed. 18: 713, 1980
Yu. I. MATVEYEVand A. A. ASKADSKII
1518
5. A. V. RAGIMOV, A. Yu. NAGIYEV, R. A. KURBANOVA, B. I. LIOGON'KII and A. A. BERLIN, Vysokomol. soyed. A21: 382, 1979 (Translated in Polymer Sci. U.S.S.R. 21: 2, 418, 1979) 6. F. TUDOS, Acta Chem. Scand. 44: 409, 1966 7. U. A. BENESI and J. U. HILDEBRAND, J. Amer. Chem. Soc. 71: 2703, 1049; J. A. A. KETELAAR, Rec. trav. chem. 71: 1104, 1952 8. T. KOKUBO, S. IWATSUKI and Y. YAMASHITO, Macromolecules 1: 482, 1968 9. S. IWATSUKI and A. ITOH, J. Polymer Sci. Polymer Chem. Ed. 18: 2971, 1980 10. A. V. RAGIMOV, A. Yu. NAGIEV, A. I. KUZAEV and B. I. LIOGONKY, Polymer 23: 1387, 1982
Polymer ScienceU.S.S.R.Vol. 28, No. 7, pp. 1518-1527, 1986 ]Printed in Poland
0032-3950/86 $10.00+.00 © 1987PergamonJournals Ltd.
FORMATION OF SUPRAMOLECULAR STRUCTURES IN AMORPHOUS POLYMERS* Yu. I. MATVEYEV a n d A. A . ASKADSKII Kuibyshev Engineering-Construction Institute, Moscow (Received 9 September 1984) A scheme of the formation of the elements of the supramolecular structure of polymers on the basis of the Lifshits theory of the "coil-globule" transition is proposed and analysed. The scheme helps to explain a number of phenomena observed experimentally during the formation of polymer bodies from solutions (the influence of the quality of the solvent on the properties, plasticization and antiplasticization, etc.) and to predict ways of obtaining polymer bodies with the desired structure and properties. THE e x p e r i m e n t a l m a t e r i a l n o w to h a n d a n d a l s o the t h e o r e t i c a l investigations o f p o l y m e r s help to m a p out a scheme o f the f o r m a t i o n o f s u p e r m o l e c u l a r structures (s.m.s.) a n d f r o m this scheme a t t e m p t to establish the link between the c h e m i c a l struc, ture o f the p o l y m e r , its s.m.s, a n d p h y s i c a l p r o p e r t i e s . T h e p r o b l e m o f the s.m.s.s a n d t h e i r forms was first f o r m u l a t e d in [1]. V a r i o u s s.m.s, m o d e l s t h e n a p p e a r e d [2, 3] h e l p i n g to explain a n u m b e r o f p r o p e r t i e s o f a m o r p h o u s p o l y m e r s in solutions, the m e l t a n d solid state. Simultaneous w i t h m o d e l concepts n u m e r o u s e x p e r i m e n t s were c a r r i e d o u t to detect the s.m.s, b y various m e t h o d s , the m o s t w i d e l y a d o p t e d being t h a t o f e l e c t r o n microscopy. T h e m o s t c h a r a c t e r i s t i c picture o b s e r v e d in a m o r p h o u s p o l y m e r s is t h a t o f globules the size o f w h i c h c o r r e s p o n d s to aggregates o f tens a n d h u n d r e d s of macromolecules. .Vysokomol. soyed. A28: No. 7, 1365-1372, 1986.