- Email: [email protected]
Kargin lectures
K a r g i n lectures
3063
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.
F. A. BOVEY, J. P o l y m e r Sci. 62: 197, 1962 F. A. ROVEY and G. V. TIYERS, K h l m l y a i tekhnol, polimerov No. 9, 3, 1964 N. HARWOOD a n d S. RITCHEY, J. P o l y m e r Sci. B3: 419, 1965 K. ITO a n d Y. YAMASHITA, J. P o l y m e r Sei. BS: 625, 1965 K. ITO, S. IWASE, K. U M E H A R A a n d Y. YA1KASHITA, J. Macromolec. Sci. A15: 891, 1967 A. JENKINS a n d M. RAYNER, Europ. P o l y m e r J. 8: 221, 1972 K. ITO and Y. YAMASHITA, K o g y o K a g a k u Zasshi SS: 1469, 1965 M. I. AGEYEV, L. S. KRIVONOS a n d Yu. I. 1KARKOV, Algoritmy, 4, ~ o . 103a, VTs A N SSSR, 1967 M. FINEMAN and S. D. ROSS, J. P o l y m e r Sci. 5: 269, 1950 A. I. YEZRIYELEYEV, E. L. BROKHINA a n d Ye. S. ROSKIN, Vysokomol. soyed, 1O: 1670, 1968 (Not t r a n s l a t e d in P o l y m e r Sci. U.S.S.R.) M. HIROOKA a n d M. YABUUCHI, J. P o l y m e r Sci. 6, A-2: 1381, 1968 L. B. STROGAN0V, Yu. A. TARAN, N. A. PLATE and T. ZEIFERT, Vysokomol. soyed. A16: 3147, 1974 (Translated in P o l y m e r Sci. U.S.S.R. 16: 9, 1974) N. M. SERGEYEV, Zh. strukt, khimii 7: 356, 1966 V. D. MOCHEL, Macromolecules 2: 537, 1969
REPORT KARGIN LECTURES* P. V. KOZLOV THE n e x t K a r g i n lectures were held on 24 J a n u a r y 1974 at the chemical faculty of the Moscow S t a t e University. These lectures were dedicated to the memory of Academician Valentin Alekseyevich Kargin, the greatest scientist of our country. The K a r g i n lectures were opened b y Acad. I. V. Petryanov-Sokolov who in his introd u c t e r y speech made a brief reference to Acad. V. A. Kargin, the scientist with an unusual range of scientific interests not only in the field of polymer science b u t also m a n y other fields of chemical knowledge. As in all previous lectures, the first p a p e r was of a memorial, nature. I t was r e a d b y N. F. Bakoyev on the theme of studies b y Aead. V. A. K a r g i n concerning polymer structure. N. F. B a k e y e v emphasized in the i n t r o d u c t o r y p a r t of his lecture t h a t V. A. K a r g i n m a d e the most significant original contribution to the modern world science of polymers in the formation and development of his teaching concerning the supermolecular structure of polymers and in the extension of structural approach and ideas to all m a i n fields of physics, physical chemistry a n d chemistry of high molecular weight compounds. N. F. B a k e y e v noted that, until the studies of V. A. Kargin a n d his school, ideas concerning p o l y m e r structure were primitive and simply untrue. The a b u n d a n t e x p e r i m e n t a l material first o b t a i n e d b y V. A, Kargin, his colleagues and pupils and then also b y several scientists b o t h in the U S S R and a b r o a d made it possible to confirm the concept concerning the struct u r a l heterogeneity of polymers, determined b y the discovery of a large v a r i e t y of fibrillar * Vysokomol. soyed. A16: No. 11, 2628-2629, 1974.
3064
P, V. K o z L o v
supermolecular formations during polymer synthesis and processing. N. F. Bakeyev dealt with details of these ideas expressed by the theory of bundle structure proposed by V. A. Kargin, A. I. Kitaigorodskii and G. L. Slonimskii for polymers in the amorphous state and the development of these ideas in papers by V. A. Kargin's pupils--S. A. Arzhakov, N. F. Bakeyev and V. A. Kabanov who developed a domain-fibrillar structural model for amorphous polymers. Further, N. F. Bakeyev dealt with studies by V. A. Kargin and his school in the field of structure and type of crystalline state of polymers. Structural features of polymers established by V. A. Kargin and his colleagues and the mutual relation between the structure and properties of polymers has led to two new trends in polymer science: structural mechanics of polymers and structural physical modification of properties of polymer materials and products. N. F. Bakeyev briefly explained these trends, their scientific significance and practical value. To conclude his paper N. F. Bakeyev dealt with structure formation during the synthesis of high molecular weight substances and the role of structural features in chemical conversion and chemical modification of polymers. N. F. Bakeyev noted in this respect that explaining the structural chemical approach to the understanding of chemical reactions with the participation of macromolecules and studying polymerization and structure formation as a single process with their mutual effect was the original and fundamental contribution of V. A. l~argin and his school to the chemistry of high molecular weight compounds. An excellent illustration of this last part of N. F. Bakeyev's paper was the paper by V. A. Kabanov, corresponding member of the U.S.S.R. Academy of Sciences entitled "Structural and Topological Aspects of Homophase Polymerization". In this paper he examined the interrelation between radical polymerization kinetics and processes of crossli-l~i-g in the polymer formed. I t was shown experimentally that some features of radical polymerization kinetics are difficult to understand without dealing with supermolecular formations in the polymer during polymerization, in spite of the apparent homogeneity of the reaction system. Structure formation may be accompanied by the "seizure" and stabilization of macroradicals. The addition of complex forming agents and the variation of temperature influence structure formation and thus reaction kinetics of homo-phase polymerization. The other three papers were concerned with some aspects of development of properties of polymer electrolytes. I n his paper by I. V. Berezin, Corresponding Member of th~ U.S.S.R. Academy of Sciences dealt with the effect of polymer matrices on the kinetics and mechanism of action of ferments and reported new results about the effect of properties of polymer substrate on the activity of ferments. Variations of physical dimensions of substrate (elongation, compression) alter the rate of fermentative processes which gives hope to find possible ways of regulating by mechanical methods the rate of catalytic reactions taking place with ferments. I n his paper I. V. Berezin dealt with prospects of using immobilized ferments to form new energy and photographic processes and to develop new analytical precision methods which may be used in many fields, particularly in clinical biochemistry. The latter is of particular importance since the indifference of the matrix in relation to elements of live organism should be observed in these analyses. In his paper entitled "Interaction of Polyelectrolytes with Ions of Organic and Physiologically Active Substances" G. V. Samsonov mainly dealt with theoretical problerns of adsorption and ion exchange using erosslinked polyelectrolytes of variable crosslinked structure. He gave convincing proof of the practical methods of developing highly effective macro-three dimensional and macro-porous ion exchange resins capable of separating complex organic molecules with exceptional selectivity and at high speed. Finally, I. M. Papisov dealt with cooperative interchain reactions of oligomer-matrix type. There are two types of equilibrium in these reactions: between free macromolecules
K a r g i n lectures
3065
a n d particles of the polycomplex a n d in polycomplex particles t h e m s e l v e s - - b e t w e e n free units a n d units t h a t h a d formed complexes (or chain segments}. Equilibrium in these reactions is determined b y t h e concentration of reagents, temperature, t y p e of reaction medium a n d molecular characteristics of reacting c h a i n s - - t h e i r microstructure, length a n d flexibility. The existence of equilibrium in similar s y s t e m s predetermines the possibility of reactions of substitution on the macromolecular level, when the macromoleculewbeing a stronger complex forming a g e n t - - d i s p l a c e s the other macromolecule from the polycomplex. A s t u d y was also m a d e of the effect of conformation transitions of macromolecules during complex formation on the distribution of oligomers between matrices a n d experimental results are given which show t h a t cases m a y occur when oligomers are distributed in similar reactions between the matrices b y the "all or nothing" principle. The cooperative interaction between the daughter chain a n d the m a t r i x is a necessary condition of m a t r i x p o l y m e r reactions--models of m a t r i x synthesis. This condition is valid at a certain stage of the m a t r i x polyreaction, when the length of the daughter chain reaches dimensions sufficient for cooperative combination with the matrix. Methods are also examined for solving the problem of controlling m a t r i x polymer reactions in 9ystems containing two or more matrices of different chemical structure. N. A. P l a t e who presided over the evening session concluding the lectures emphasized t h a t this forum of scientists clearly demonstrated the increasing role of a new v e r y promising t r e n d in modern polymer s c i e n c e - - t h e chemistry and physical chemistry of bio-active macromoleeules a n d the close relation between the purely chemical aspects of reaction mechanisms and structural problems of the chemistry of high molecular weight compounds. The studies m a d e in this direction on the foundations laid down b y V. A. K a r g i n were m a r k e d b y several significant achlevments in recent years. Transla?~ by E. S~.~RE
3063
REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.
F. A. BOVEY, J. P o l y m e r Sci. 62: 197, 1962 F. A. ROVEY and G. V. TIYERS, K h l m l y a i tekhnol, polimerov No. 9, 3, 1964 N. HARWOOD a n d S. RITCHEY, J. P o l y m e r Sci. B3: 419, 1965 K. ITO a n d Y. YAMASHITA, J. P o l y m e r Sei. BS: 625, 1965 K. ITO, S. IWASE, K. U M E H A R A a n d Y. YA1KASHITA, J. Macromolec. Sci. A15: 891, 1967 A. JENKINS a n d M. RAYNER, Europ. P o l y m e r J. 8: 221, 1972 K. ITO and Y. YAMASHITA, K o g y o K a g a k u Zasshi SS: 1469, 1965 M. I. AGEYEV, L. S. KRIVONOS a n d Yu. I. 1KARKOV, Algoritmy, 4, ~ o . 103a, VTs A N SSSR, 1967 M. FINEMAN and S. D. ROSS, J. P o l y m e r Sci. 5: 269, 1950 A. I. YEZRIYELEYEV, E. L. BROKHINA a n d Ye. S. ROSKIN, Vysokomol. soyed, 1O: 1670, 1968 (Not t r a n s l a t e d in P o l y m e r Sci. U.S.S.R.) M. HIROOKA a n d M. YABUUCHI, J. P o l y m e r Sci. 6, A-2: 1381, 1968 L. B. STROGAN0V, Yu. A. TARAN, N. A. PLATE and T. ZEIFERT, Vysokomol. soyed. A16: 3147, 1974 (Translated in P o l y m e r Sci. U.S.S.R. 16: 9, 1974) N. M. SERGEYEV, Zh. strukt, khimii 7: 356, 1966 V. D. MOCHEL, Macromolecules 2: 537, 1969
REPORT KARGIN LECTURES* P. V. KOZLOV THE n e x t K a r g i n lectures were held on 24 J a n u a r y 1974 at the chemical faculty of the Moscow S t a t e University. These lectures were dedicated to the memory of Academician Valentin Alekseyevich Kargin, the greatest scientist of our country. The K a r g i n lectures were opened b y Acad. I. V. Petryanov-Sokolov who in his introd u c t e r y speech made a brief reference to Acad. V. A. Kargin, the scientist with an unusual range of scientific interests not only in the field of polymer science b u t also m a n y other fields of chemical knowledge. As in all previous lectures, the first p a p e r was of a memorial, nature. I t was r e a d b y N. F. Bakoyev on the theme of studies b y Aead. V. A. K a r g i n concerning polymer structure. N. F. B a k e y e v emphasized in the i n t r o d u c t o r y p a r t of his lecture t h a t V. A. K a r g i n m a d e the most significant original contribution to the modern world science of polymers in the formation and development of his teaching concerning the supermolecular structure of polymers and in the extension of structural approach and ideas to all m a i n fields of physics, physical chemistry a n d chemistry of high molecular weight compounds. N. F. B a k e y e v noted that, until the studies of V. A. Kargin a n d his school, ideas concerning p o l y m e r structure were primitive and simply untrue. The a b u n d a n t e x p e r i m e n t a l material first o b t a i n e d b y V. A, Kargin, his colleagues and pupils and then also b y several scientists b o t h in the U S S R and a b r o a d made it possible to confirm the concept concerning the struct u r a l heterogeneity of polymers, determined b y the discovery of a large v a r i e t y of fibrillar * Vysokomol. soyed. A16: No. 11, 2628-2629, 1974.
3064
P, V. K o z L o v
supermolecular formations during polymer synthesis and processing. N. F. Bakeyev dealt with details of these ideas expressed by the theory of bundle structure proposed by V. A. Kargin, A. I. Kitaigorodskii and G. L. Slonimskii for polymers in the amorphous state and the development of these ideas in papers by V. A. Kargin's pupils--S. A. Arzhakov, N. F. Bakeyev and V. A. Kabanov who developed a domain-fibrillar structural model for amorphous polymers. Further, N. F. Bakeyev dealt with studies by V. A. Kargin and his school in the field of structure and type of crystalline state of polymers. Structural features of polymers established by V. A. Kargin and his colleagues and the mutual relation between the structure and properties of polymers has led to two new trends in polymer science: structural mechanics of polymers and structural physical modification of properties of polymer materials and products. N. F. Bakeyev briefly explained these trends, their scientific significance and practical value. To conclude his paper N. F. Bakeyev dealt with structure formation during the synthesis of high molecular weight substances and the role of structural features in chemical conversion and chemical modification of polymers. N. F. Bakeyev noted in this respect that explaining the structural chemical approach to the understanding of chemical reactions with the participation of macromolecules and studying polymerization and structure formation as a single process with their mutual effect was the original and fundamental contribution of V. A. l~argin and his school to the chemistry of high molecular weight compounds. An excellent illustration of this last part of N. F. Bakeyev's paper was the paper by V. A. Kabanov, corresponding member of the U.S.S.R. Academy of Sciences entitled "Structural and Topological Aspects of Homophase Polymerization". In this paper he examined the interrelation between radical polymerization kinetics and processes of crossli-l~i-g in the polymer formed. I t was shown experimentally that some features of radical polymerization kinetics are difficult to understand without dealing with supermolecular formations in the polymer during polymerization, in spite of the apparent homogeneity of the reaction system. Structure formation may be accompanied by the "seizure" and stabilization of macroradicals. The addition of complex forming agents and the variation of temperature influence structure formation and thus reaction kinetics of homo-phase polymerization. The other three papers were concerned with some aspects of development of properties of polymer electrolytes. I n his paper by I. V. Berezin, Corresponding Member of th~ U.S.S.R. Academy of Sciences dealt with the effect of polymer matrices on the kinetics and mechanism of action of ferments and reported new results about the effect of properties of polymer substrate on the activity of ferments. Variations of physical dimensions of substrate (elongation, compression) alter the rate of fermentative processes which gives hope to find possible ways of regulating by mechanical methods the rate of catalytic reactions taking place with ferments. I n his paper I. V. Berezin dealt with prospects of using immobilized ferments to form new energy and photographic processes and to develop new analytical precision methods which may be used in many fields, particularly in clinical biochemistry. The latter is of particular importance since the indifference of the matrix in relation to elements of live organism should be observed in these analyses. In his paper entitled "Interaction of Polyelectrolytes with Ions of Organic and Physiologically Active Substances" G. V. Samsonov mainly dealt with theoretical problerns of adsorption and ion exchange using erosslinked polyelectrolytes of variable crosslinked structure. He gave convincing proof of the practical methods of developing highly effective macro-three dimensional and macro-porous ion exchange resins capable of separating complex organic molecules with exceptional selectivity and at high speed. Finally, I. M. Papisov dealt with cooperative interchain reactions of oligomer-matrix type. There are two types of equilibrium in these reactions: between free macromolecules
K a r g i n lectures
3065
a n d particles of the polycomplex a n d in polycomplex particles t h e m s e l v e s - - b e t w e e n free units a n d units t h a t h a d formed complexes (or chain segments}. Equilibrium in these reactions is determined b y t h e concentration of reagents, temperature, t y p e of reaction medium a n d molecular characteristics of reacting c h a i n s - - t h e i r microstructure, length a n d flexibility. The existence of equilibrium in similar s y s t e m s predetermines the possibility of reactions of substitution on the macromolecular level, when the macromoleculewbeing a stronger complex forming a g e n t - - d i s p l a c e s the other macromolecule from the polycomplex. A s t u d y was also m a d e of the effect of conformation transitions of macromolecules during complex formation on the distribution of oligomers between matrices a n d experimental results are given which show t h a t cases m a y occur when oligomers are distributed in similar reactions between the matrices b y the "all or nothing" principle. The cooperative interaction between the daughter chain a n d the m a t r i x is a necessary condition of m a t r i x p o l y m e r reactions--models of m a t r i x synthesis. This condition is valid at a certain stage of the m a t r i x polyreaction, when the length of the daughter chain reaches dimensions sufficient for cooperative combination with the matrix. Methods are also examined for solving the problem of controlling m a t r i x polymer reactions in 9ystems containing two or more matrices of different chemical structure. N. A. P l a t e who presided over the evening session concluding the lectures emphasized t h a t this forum of scientists clearly demonstrated the increasing role of a new v e r y promising t r e n d in modern polymer s c i e n c e - - t h e chemistry and physical chemistry of bio-active macromoleeules a n d the close relation between the purely chemical aspects of reaction mechanisms and structural problems of the chemistry of high molecular weight compounds. The studies m a d e in this direction on the foundations laid down b y V. A. K a r g i n were m a r k e d b y several significant achlevments in recent years. Transla?~ by E. S~.~RE