- Email: [email protected]
IInd All-Union conference on the chemistry and physico-chemistry of oligomers
~100
S . M . MEzmKOVSKII a n d D. B. I z ~ o v REFERENCES
1. Ye. M. PEREPLETCHIKOVA, E. G. POMERANTSEV, L. A. TSAREVA, G. V. ANDREYEVA and E. O. KRATS, Plast. massy, No. 8, 71, 1972 2. G. P. FRA]KTINA (book), Metody issledovaniya udaroprochnykh polistirolov (Methods of Investigating High-impact Polystyrene). Izd. " K h i m i y a " , 1975 3. N . A . ISAKOVA, V. S. FTKHTENGOL'TS and V. M. KRASIKOVA, Metody issledovaniya sostava elastomerov (Methods of Investigating Elastomer Composition). Izd. " K h i m i y a " , 1974 4. Ye. I. KRASNOVA, V. B. KONSULOV, I. B. KT.TMENKO, A. N. SAVITSKAYA and L. A. VOL'F, Zh. prikh khimii 49: 903, 1976 5. T. A. BELOUSOVA, G. D. L1TOVCHENKO and N. V. MIKHAILOV, Khimich. volokna, No. 5, 43, 1971 6. M. P. ZVEREV, Khimich. volokna, No. 5, 3, 1975 7. G. D. LITOVCHENKO, A. N. BARASH, M. P. ZVEREV and N. F. KALYANOVA, Zh. prikl, spektroskopii 29: 68, 1978
]Polymer ScienceU.S.S.R. Vo]. 22, No. 8, pp. 2100-2105, 1980 Printed in Poland
0082-3950/80/082100-061~7.59/0 © 1981 Pergamon M
Ltd.
REPORTS lind ALL-UNION CONFERENCE ON THE CHEMISTRY AND PHYSICOoC~MISTRY OF OLICOMERS* S. M. MEZHIKOVSKII a n d D . B . IzYUMOV
THs I I n d All-Union Conference on the Chemistry and Physico-chemistry of Oligomers, organized b y the Scientific Council on H i g h Molecular Weight Compounds, U.S.S.R. A c a d e m y of S~iences, the I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences, the I n s t i t u t e of Chemical Sciences, Kaz.S.S.R. Academy of Sciences and the Ukrainian Scientific Research I n s t i t u t e of Plastics, U.S.S.R. Ministry of Chemical Industry, was held between 22 and 25 October, 1979 in Alma-Ata. The Conference was opened b y Acad. N. S. Yenikolopyan. He noted t h a t about 25% of the world's production of polymeric materials is now based on the use of oligomers t h a t can undergo polymerization therefore, a discussion of general problems of chemistry, physics, physico-chemistry and technology, which are common for all types of oligomer and materials prepared from them, will contribute to the successful development of the science of polymers as a whole. Acad. N. S. Yenikolopyan then emphasized t h a t devoting the I I n d AU-Union Conference of Oligomers to the m e m o r y of Al'fred Anisimovich Berlin, the eminent Soviet scientist is a recognition of his great service to establishing and developing the oligomer field as a separate scientific trend. Main trends developed b y Prof. A. A. Berlin in the field of the chemistry of polyreactive oligomers and polymers prepared from t h e m were reflected in a 'special paper b y T. Ya. * Vyaokomol. s o y e d . A ~ : No. 8, 1913-1916, 1980.
I I n d All.Union Conference on Chemistry of Oligomers
2101
Kefeli. A detailed s t u d y was made, in particular, of condensation telomerization, a m e t h o d which formed the foundation of the industrial synthesis of structurally regular unsaturated oligomers with a given t y p e of oligomer unit and a given t y p e and number of functional groups. Studies were also examined b y A. A. Berlin concerning the mechanism and kinetics of three-dimensional polymerization of oligomers and the relation between oligomer structure a n d properties of polymer. Considerable attention was given in the paper to aspects of using oligomers for obtaining sealants, adhesives, electric insulating compounds, filled and reinforced plastics, etc. The p a p e r also dealt with studies b y A. A. Berlin concerning '~temporary plasticization", gas-expanded polymers, investigations in the field of the chemistry of polyconjugated systems, etc. The lecturer emphasized the enormous effect of fundamental studies b y A. A. Berlin on the development of modern science and i n d u s t r y of oligomers. A wide range of problems was discussed at the Conference, which dealt with the determination of the oligomer state, physico-chemistry of oligomers, molecular a n d supermoleeular structure, kinetics and mechanism of oligomer conversion into linear and crosslinked polymers, thermodynamics of oligomer and polymer-oligomer compounds, formulation and fields of application of oligomers, etc. 167 oral and stand reports were given and discussed at three plenary and six sectional meetings and these were presented b y 80 Institutes and Organizations. The first plenary session was concerned with the physico-chemistry of oligomers. I n their paper E. F. Weinstein, V. M. K o m a r o v and L. V. Klochkova (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) made an a t t e m p t to divide homologous series into low molecular weight compounds, oligomers and polymers b y m a t h e m a t i c a l simulation of a chain molecule using distribution according to Gibbs energies of conformers with different local rigidities. I t was shown t h a t a specific feature of oligomers is the varying likelihood of distribution of conformers along the chain, while for low molecular weight compounds and polymers all places along the chain are equivalent. Results of calculations o f conformations, oligotetramethylene- and oligo-hydroxypropylene glycol chains using the method of a t o m - a t o m potentials were described b y V. V. Shilov, N. Ye. K r u g l y a k a n d Yu. S. L i p a t o v (Institute of the Chemistry of High-Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences). Using these results and d a t a of broad-angle X - r a y scattering in liquid oligomers the authors examined the short-range ordering of the oligomers studied a n d gave an interpretation within the framework of the isomer model. S. M. Domakin, R. M. Aseyeva and G. Ye. Zaikov (Institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences) calculated thermodynamic characteristics of dimethacrylic oligomer homologues of alkylene- a n d hydroxyalkylene glycols. The t y p e of crystallization of oligodiene urethane epoxides was examined in a paper b y S. S. Vladimirov et al. ( K I S I a n d V N I I S K ) , while the identity of supermolecular formations in liquid dimethacrylic esters of oligoethylene glycols a n d three-dimensional polymers prep a r e d from them, in a paper b y N. G. Matveyeva et a/. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences and I n s t i t u t e of Physical Chemistry, U.S.S.R. A c a d e m y of Sciences). Considerable interest was attached to a series of papers dealing with the use of chromatographic methods for the analysis of oligomers. I n a paper b y P. P. Nefedov et s/. (Institute of H i g h Molecular Weight Compounds, U.S.S.R. Academy of Sciences) methods were proposed for calculating molecular weight distribution, average molecular weights and heterogeneity coefficients according to results of exclusion liquid chromatography. Various modifications of adsorption and gel-permeation chromatography as a method of investigating molecular weight distribution and distribution according to the t y p e of functionality of oligomers were used in studies b y S. G. Entelis et ed. (institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences), A. S. Skvortsov et al. (Institute of High-Molecular Weight Compounds, U.S.S.R. A c a d e m y of Sciences), G. V. Lyubimova, et at. (Institute of Chemical Physics, U.S.S.R:
2102
S. M. ME~rlrOVSKII and D. B. IzY~rMov
Academy of Sciences}, R. A. Shlyakhter ~ aJ. (All-Union Scientific Research Institute for Synthetic Rubber), A. I. Kuzayev and S. M. Baturin (ONKhF, U.S.S.R. Academy of Sciences), Ye. N. Barantsevich ~ al. (All-Union Scientific Research Institute for Synthetic Rubber); the four last papers were also concerned with various approaches to controlling the molecular heterogeneity of products during synthesis and to obtaining oligomers with a given molecular structure. The second plenary session was concerned with the analysis of the molecular structure of three-dimensional polymers and the:problem of decomposition of networks. A typical feature of studies in this direction was the variety of physical methods used b y the authors for the experimental study of the molecular structure of networks. Light scattering and electron miscroscopy were used by L. M. Bogdanovskii et al. (OIKhF, U.S.S.R. Academy of Sciences) for the study of the formation of three-dimensional structures based on epoxy-diamines. A paper by V. G. Shevchenko et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) dealt with the use of electric methods for the study of molecular mobility during the formation of epoxy-amine networks. I R spectroscopy was used by L. V. Vladimirov and E. F. Oleinik (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) for the investigation of similar systems. A complex of methods (radiothermoluminescenee, differential scanning calorimetry and heat-stimulated depolarization) was used for the analysis of structure in other studies by E. F. Oleinik. The NMR pulse method was applied for the study of relaxation characteristics of epoxy-amine (I. N. Zakirov et al., KISI) and polyester urethane (V. S. Minkin et al., K K h T I ) networks and the paramagnetic probe method for the evaluation of segmental mobility of polydiene urea urethanes (L. I. Dashevskii, S. M. K a v u n and A. S. Lykin, NIIShP). Papers were also presented, in which calculations concerning models were compared with the experiment. For example, in a study by R. A. Turusov et al. (ONKhF U.S.S.R. Academy of Sciences) a model of a hollow sphere was used for the study of mechanical effects in frontal solidification of oligomers and an equation was proposed for calculating residual stress in the material. Calculations were made in a paper b y V. P. Roshupkin (OIKhF, U.S.S.R. Academy of Sciences) concerning polymerization stress and structural features and properties of polyesteracrylates, dependent on specific features of thermodynamics of trimerization, analysed. The stage of solidification of polyesteracrylates as a process of the "second gel-point" was examined in a paper by M. P. Berezin and G. V. Korolev (OIKhF, U.S.S.R. Academy of Sciences). A paper b y a large group of authors (E. V. Prut) (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) was concerned with a statistical model of crosslinked polymer structures; this model enabled a quantitative relation to be established between the chemical structure of initial epoxy oligomers, the formation, technical structure and equilibrium physico-mechanical properties of densely crosslinked networks. Papers were read at the final plenary session which were concerned with the various aspects of using oligomers as coatings (L. A. Bakalo et al., IOKh, Ukr.S.S.R. Academy o f Sciences and I K h D , Latv.S.S.R. Academy of Sciences, A. D. Yeselev et al. G I P I LKP), sealants for electrical (S. I. Makarenko et al., KhPI) and constructional (L. M. Demchenko et ~ . , VNIIstroipolimer) purposes, photoconductive films (A. Ya. Veiner et al., N I I O P i K ) , matrices for galvanic copying (R. A. Zakhidov et al., T s P K T B Uzb. S.S.R. Academy of Sciences), printed forms (E. G. Lazarenko et al., Ukrainian Printing Institute), ion-exchange membranes (A. K. Chalov et al., I K h N Kaz.S.S.R. Academy of Sciences), gas-expanded polymers (F. A. Shutov et al., LISI, K. M. Gibov et al., I K h N , Kaz.S.S.R. Academy of Sciences}, glass-fibre reinforced plastics (V. Ye. Bakhareva et al., TsNIITS), etc. A special sectional meeting was concerned with kinetics and the reaction mechanism of oligomers to form linear and crosslinked polymers. Problems of interaction between di-isoeyanates and glycols and triols were dealt with in papers b y S. M. Baturin ~ al. ( O N K h F
I I n d All-Union Conference on Chemistry of Oligomers
"2103
U.S.S.R. Academy of Sciences). Reactions of di-isocyanates with oligotriols a n d oligobutadienodiols wore described in papers b y P. A. Kirpichnikov et al. ( K K h T I ) and Yo. V. Stovbun a n d V. V. Grigor'yeva (O~TKhF U.S.S.R. A c a d e m y of Sciences). Another approach to the formation of crosslinked polyurethanes was described in the paper of L. Yu. R u m y a n t s e v a n d L. I. Golovko (Institute of the Chemistry of High Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences): tri-isocyanate was solidified using alicyclic oligoester. Polymerization of oligourethane acrylates was examined in a paper b y P. V. Datsko and S. S. Gudzer (Institute of the Chemistry of H i g h Molecular Weight Compounds, Ukr.S.S.R A c a d e m y of Sciences}. Specific features of polymerization of oligoester acrylates were examined b y D. A. Aronovich et al. (NIIpolimerov), B. V. Ozerkovskii and V. P. Roshupkina ( O N K h F U.S.S.R. A c a d e m y of Sciences), I. M. Al'shits et ed. (TsNIITS), N. N. Tvorogova a n d I. A. Matveyeva (Institute of Chemical Physics, U.S.S.R. Academy of Sciences}. Solidification of various oligoestermaleate fumarates was examined b y G. P. Zubar' and V. V. Popova (KhPI), Ye. G. Zil'berman et al. (NIIPM). Among papers devoted to network-formation taking place with the opening of epoxy rings greatest attention was a t t r a c t e d b y papers of 0. B. Salamatina et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences}, M. K. P a k t e r et al. (UkrNIIPM), N. K. Moshinskaya et al. (DKhTI), M. F. Sorokina e~ al. (MKhTI), Ye. Ye. Yergozhina, et 02. (IKh!q Kaz.S.S.R. Academy of Sciences), M. F. Sorokina et ed. (MKhTI), Ye. Ye. Yorgozhina et o2. ( I K h N Kaz.S.S.R. A c a d e m y of Sciences) and a series of studies carried out u n d e r the guidance of B. A. Rozenberg (ONKhF, U.S.S.R. Academy of Sciences) and V. N. N i k o l a y e v a (LTI). Papers dealing with the effect of various fields of force on the solidification of oligomers a n d the structure of three-dimensional products formed iV. O. Khozin e$ a/., K I S I ; M. S. Trizno et al., LTI; T. A. K o l ' t s o v a a n d M. S. Akutin, M K h T I , and others) produced livorly discussions. A separate session was devoted to oligomers, the solidification of which produced heat-resistant polymers (oligomers with a conjugated systems and hereto-organic oligomers). A report b y B. 2. Zapadinskii et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) examined results of studying kinetics and the mechanism of formation of oligo(arylenebisbenzimidazoles), their copolymerization with oligoimides and properties of materials based on them. A paper b y Ya. S. Vygodskii et al. (Institute of Hotero-organic Compounds, U.S.S.R. A c a d e m y of Sciences) dealt with crosslinked polymers based on bis-maleimides and cardo-diamines. Various aspects of modification of oligoimides and their polymeri. zation were dealt with in the papers b y G. I. Boiko et al., Zh. Zh. Boyarstanova et al., N . P . Lyubchenko et al. (Institute of Chemical Physics, Kaz.S.S.R. Academy of Sciences); T. S. Tsyganov et al. (Institute of High Molecular Weight Compounds, U.S.S.R. Academy of Sciences); A. I. Mikhal'skii et al. (VIAM); A, I. Volozhin (IFOS, B.S.S.R. A c a d e m y of Sciences) and others. Polyheterearylenes prepared b y isomerizatien ring formation of polycyanurea based on oligomers with aminonitrile end groups and amino-groups were examined b y E. N. Telosheva et al, ( N I F K h I ) , P. M. Valetskii et al. (INEOS U.S.S.R. Academy of Sciences and Moscow Chemico-Teehnological Institute), G. I. Tsvelikhovskii et al. (VNIIEUI), V. K. Skachkova et al., V. A. Grigorovskaya et al. (Institute of Chemical Physics, U.S.S.R. Acad e m y of Sciences} described the structure, properties, special features of network formation of different oligoheteroarylenes a n d materials based on them. New oligomors with t e r n a r y terminal bonds, allene oligomers and oligomors prepared b y motothesis were reported b y A. I. Shorle e$ ag. (Institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences}, V. A. Bunin et al. ( O I K h F , U.S.S.R. Academy of Sciences). Yu. V. K o r s h a k (INKhS, U.S.S.R. Academy of Sciences).
2104
S. M. M~.ZH~OVSXII and D. B. I z r t ~ o v
Organosilicon compounds were dealt with in most detail of all hetero.organic oligomers. A paper b y I. A. Vostokov and Yu. I. D e r g u n o v (DF GIAP) was concerned with organosilicon earbodi-imide oligomers. Polyorganosiloxanes with peroxidate functional groups were described in a paper b y A. K. Likovets et aL (LPI). A paper b y L. M. Khananashvili ¢t aL (Tbilisi State University) dealt with polyorganosiloxanes with dicyclopentaenyl radicals a t the silicon atom. A paper b y V. P. Misina et al. (Institute of Heteroorganic Compounds, U.S.S.R. A c a d e m y of Sciences) examined the reactivity of carboflmctional oligosiloxanediols in reactions with phenylisocyanate. Three meetings of the section of oligomer and polymer-oligomer mixtures were d o v o t ~ to main problems of thermodynamics of blending, conversion mechanisms and the structure of composites and properties of solidified multi-component materials. There was a lively and fruitful discussion a t the conference concerning the phase condition of polymer-oligomer mixtures. Papers were devoted, in particular, to the free energy variation of mixing b y the sorption method (T. V. Ikanina, et al. Urals State University), determining the Huggins constant b y the method of inversion of gas chromatography (Yu. S. L i p a t o v and A. Ye. Nesterov, IKhVS, Ukr.S.S.R. Academy of Sciences), calculating thermodynamic parameters, results of the microinterference method (a series of studies b y A. Ye. Chalykh carried out jointly b y the I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences and I N K h F , U.S.S.R. Academy of Sciences), thermo-rheological curves (Ye. V. Khabarov, et al. N I I R P ) , deviation from a d d i t i v i t y of optical properties of mixtures (S. A. Yaroshevskii et al., U k r N I I P M ; T. I. R a d b i l ' et al., l~IIpolimerov), evaluating rates of solution (B. S. Grishin et al., N I I S h P and I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences), microcalorimetric d a t a (E. F. Wainstein, et al. Institute of Chemical Physics, Ukr.S.S.R. Academy of Sciences) and others. The interpretation of results obtained within the framework of the F l o r y - H u g g i n s , F i e r y - P a t t e r s o n theory and comparison of thermodynamic parameters of the condition of the system with physico-mechanical and technological properties show t h a t the phase condition at different stages of conversion of the multi-component system and regularities of approximation to the equilibrium state is a necessary condition of obtaining materials with given properties. Phase equilibrium was compared in a number of papers with the molecular ar_d supermolecular structure of composites. F o r example, in a paper b y Yu. P. Toms and V. V. Shilov (IKhVS, Ukr.S.S.R. A c a d e m y of Sciences) the structural heterogeneity of oligo-oxymothylene-, ethylene- and propyleneglycol mixtures studied b y wide-angle and small-angle X - r a y diffractometry was compared with thermodynamic parameters of interaction of components. When studying the molecular mobility of polymer-oligomer systems of the oligoesteracryla t e - - p o l y m e r m a t r i x t y p e in the glassy and high-elastic state T. I. Borisova et al. (Institute o f H i g h Molecular Weight Compounds, U.S.S.R. Academy of Sciences and I n s t i t u t e of Chemical Physics, U.S.S.R. Academy of Sciences) differentiated relaxation transitions in connection with the phase equilibrium of the system. The structure of solidified rubber-oligomer compositions was examined b y T. D. Mal'chevskaya et al. (NIIRP), V. S. Derinovskii et aL ( K I S I and O I K h F , U.S.S.R. Academy of Sciences), D. B. Boguslavskii et al. (DF N I I S h P ) , R. Sh. Frenkel' et al. ( V N I K T I R P ) . A s t u d y was made of the effect of the t y p e of oligomer on the structure and proper~iea of polyvinylehloride b y D. B. I z y u m o v et al. (Institute of Chemical Physics, U.S.S.R. Acad e m y of Sciences), P. A. Sukhopar, B. G. Zadontseva et al. (Ukr.NIIPM), M. L. K e r b e r et al. (MKhTI). I m p o r t a n t aspects of the kinetics and mechanism of linear and three-dimensional polymerization of oligomer compounds of different chemical structure were presented b y Yo. V. K h a b a r o v a e t a / . (NIIRP), F. R. Gritsenko (Institute of the Chemistry of High Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences), V. F. Popov and V. V. Van'kovieh
I I n d All-Union Conference on Chemistry of Oligomers
2105
(:NIISHP), Yu. R. Ebich et al. (DI~hTI). A paper by T. Ye. Lipatova et al. (IOKh, Ukr.S.S 1~ Academy of Sciences) dealt with the formation of mutually penetrating networks. One of the sectional meetings also examined technical, formulating and other applied aspects of oligomer and polymer-oligomer compounds. Technical and economic problems involved in the production and application of oligomer materials in the n a t i o n a l economy were raised in a special paper b y I. M. Shologon and V. B. Byalykh (UkrNIIPM). I t was noted in the discussion of this paper that technical and economic foundations have not, so far, become widespread enough in oligomer technology. The Conference summarized theoretical and applied problems raised during recent years in the field of oligomers and noted the main trends in subsequent investigations. The resolution passed at the Conference plamled to take a n u m b e r of measures aimed at the speedy introduction of scientific research into the practice of industrial enterprises and at the improvement of training specialists in the field of oligomer technology. I t is planned to hold the I I I r d All-Union Conference on oligomers in Kiev in 1982. Translated by E. SEY~.~RE
S . M . MEzmKOVSKII a n d D. B. I z ~ o v REFERENCES
1. Ye. M. PEREPLETCHIKOVA, E. G. POMERANTSEV, L. A. TSAREVA, G. V. ANDREYEVA and E. O. KRATS, Plast. massy, No. 8, 71, 1972 2. G. P. FRA]KTINA (book), Metody issledovaniya udaroprochnykh polistirolov (Methods of Investigating High-impact Polystyrene). Izd. " K h i m i y a " , 1975 3. N . A . ISAKOVA, V. S. FTKHTENGOL'TS and V. M. KRASIKOVA, Metody issledovaniya sostava elastomerov (Methods of Investigating Elastomer Composition). Izd. " K h i m i y a " , 1974 4. Ye. I. KRASNOVA, V. B. KONSULOV, I. B. KT.TMENKO, A. N. SAVITSKAYA and L. A. VOL'F, Zh. prikh khimii 49: 903, 1976 5. T. A. BELOUSOVA, G. D. L1TOVCHENKO and N. V. MIKHAILOV, Khimich. volokna, No. 5, 43, 1971 6. M. P. ZVEREV, Khimich. volokna, No. 5, 3, 1975 7. G. D. LITOVCHENKO, A. N. BARASH, M. P. ZVEREV and N. F. KALYANOVA, Zh. prikl, spektroskopii 29: 68, 1978
]Polymer ScienceU.S.S.R. Vo]. 22, No. 8, pp. 2100-2105, 1980 Printed in Poland
0082-3950/80/082100-061~7.59/0 © 1981 Pergamon M
Ltd.
REPORTS lind ALL-UNION CONFERENCE ON THE CHEMISTRY AND PHYSICOoC~MISTRY OF OLICOMERS* S. M. MEZHIKOVSKII a n d D . B . IzYUMOV
THs I I n d All-Union Conference on the Chemistry and Physico-chemistry of Oligomers, organized b y the Scientific Council on H i g h Molecular Weight Compounds, U.S.S.R. A c a d e m y of S~iences, the I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences, the I n s t i t u t e of Chemical Sciences, Kaz.S.S.R. Academy of Sciences and the Ukrainian Scientific Research I n s t i t u t e of Plastics, U.S.S.R. Ministry of Chemical Industry, was held between 22 and 25 October, 1979 in Alma-Ata. The Conference was opened b y Acad. N. S. Yenikolopyan. He noted t h a t about 25% of the world's production of polymeric materials is now based on the use of oligomers t h a t can undergo polymerization therefore, a discussion of general problems of chemistry, physics, physico-chemistry and technology, which are common for all types of oligomer and materials prepared from them, will contribute to the successful development of the science of polymers as a whole. Acad. N. S. Yenikolopyan then emphasized t h a t devoting the I I n d AU-Union Conference of Oligomers to the m e m o r y of Al'fred Anisimovich Berlin, the eminent Soviet scientist is a recognition of his great service to establishing and developing the oligomer field as a separate scientific trend. Main trends developed b y Prof. A. A. Berlin in the field of the chemistry of polyreactive oligomers and polymers prepared from t h e m were reflected in a 'special paper b y T. Ya. * Vyaokomol. s o y e d . A ~ : No. 8, 1913-1916, 1980.
I I n d All.Union Conference on Chemistry of Oligomers
2101
Kefeli. A detailed s t u d y was made, in particular, of condensation telomerization, a m e t h o d which formed the foundation of the industrial synthesis of structurally regular unsaturated oligomers with a given t y p e of oligomer unit and a given t y p e and number of functional groups. Studies were also examined b y A. A. Berlin concerning the mechanism and kinetics of three-dimensional polymerization of oligomers and the relation between oligomer structure a n d properties of polymer. Considerable attention was given in the paper to aspects of using oligomers for obtaining sealants, adhesives, electric insulating compounds, filled and reinforced plastics, etc. The p a p e r also dealt with studies b y A. A. Berlin concerning '~temporary plasticization", gas-expanded polymers, investigations in the field of the chemistry of polyconjugated systems, etc. The lecturer emphasized the enormous effect of fundamental studies b y A. A. Berlin on the development of modern science and i n d u s t r y of oligomers. A wide range of problems was discussed at the Conference, which dealt with the determination of the oligomer state, physico-chemistry of oligomers, molecular a n d supermoleeular structure, kinetics and mechanism of oligomer conversion into linear and crosslinked polymers, thermodynamics of oligomer and polymer-oligomer compounds, formulation and fields of application of oligomers, etc. 167 oral and stand reports were given and discussed at three plenary and six sectional meetings and these were presented b y 80 Institutes and Organizations. The first plenary session was concerned with the physico-chemistry of oligomers. I n their paper E. F. Weinstein, V. M. K o m a r o v and L. V. Klochkova (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) made an a t t e m p t to divide homologous series into low molecular weight compounds, oligomers and polymers b y m a t h e m a t i c a l simulation of a chain molecule using distribution according to Gibbs energies of conformers with different local rigidities. I t was shown t h a t a specific feature of oligomers is the varying likelihood of distribution of conformers along the chain, while for low molecular weight compounds and polymers all places along the chain are equivalent. Results of calculations o f conformations, oligotetramethylene- and oligo-hydroxypropylene glycol chains using the method of a t o m - a t o m potentials were described b y V. V. Shilov, N. Ye. K r u g l y a k a n d Yu. S. L i p a t o v (Institute of the Chemistry of High-Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences). Using these results and d a t a of broad-angle X - r a y scattering in liquid oligomers the authors examined the short-range ordering of the oligomers studied a n d gave an interpretation within the framework of the isomer model. S. M. Domakin, R. M. Aseyeva and G. Ye. Zaikov (Institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences) calculated thermodynamic characteristics of dimethacrylic oligomer homologues of alkylene- a n d hydroxyalkylene glycols. The t y p e of crystallization of oligodiene urethane epoxides was examined in a paper b y S. S. Vladimirov et al. ( K I S I a n d V N I I S K ) , while the identity of supermolecular formations in liquid dimethacrylic esters of oligoethylene glycols a n d three-dimensional polymers prep a r e d from them, in a paper b y N. G. Matveyeva et a/. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences and I n s t i t u t e of Physical Chemistry, U.S.S.R. A c a d e m y of Sciences). Considerable interest was attached to a series of papers dealing with the use of chromatographic methods for the analysis of oligomers. I n a paper b y P. P. Nefedov et s/. (Institute of H i g h Molecular Weight Compounds, U.S.S.R. Academy of Sciences) methods were proposed for calculating molecular weight distribution, average molecular weights and heterogeneity coefficients according to results of exclusion liquid chromatography. Various modifications of adsorption and gel-permeation chromatography as a method of investigating molecular weight distribution and distribution according to the t y p e of functionality of oligomers were used in studies b y S. G. Entelis et ed. (institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences), A. S. Skvortsov et al. (Institute of High-Molecular Weight Compounds, U.S.S.R. A c a d e m y of Sciences), G. V. Lyubimova, et at. (Institute of Chemical Physics, U.S.S.R:
2102
S. M. ME~rlrOVSKII and D. B. IzY~rMov
Academy of Sciences}, R. A. Shlyakhter ~ aJ. (All-Union Scientific Research Institute for Synthetic Rubber), A. I. Kuzayev and S. M. Baturin (ONKhF, U.S.S.R. Academy of Sciences), Ye. N. Barantsevich ~ al. (All-Union Scientific Research Institute for Synthetic Rubber); the four last papers were also concerned with various approaches to controlling the molecular heterogeneity of products during synthesis and to obtaining oligomers with a given molecular structure. The second plenary session was concerned with the analysis of the molecular structure of three-dimensional polymers and the:problem of decomposition of networks. A typical feature of studies in this direction was the variety of physical methods used b y the authors for the experimental study of the molecular structure of networks. Light scattering and electron miscroscopy were used by L. M. Bogdanovskii et al. (OIKhF, U.S.S.R. Academy of Sciences) for the study of the formation of three-dimensional structures based on epoxy-diamines. A paper by V. G. Shevchenko et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) dealt with the use of electric methods for the study of molecular mobility during the formation of epoxy-amine networks. I R spectroscopy was used by L. V. Vladimirov and E. F. Oleinik (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) for the investigation of similar systems. A complex of methods (radiothermoluminescenee, differential scanning calorimetry and heat-stimulated depolarization) was used for the analysis of structure in other studies by E. F. Oleinik. The NMR pulse method was applied for the study of relaxation characteristics of epoxy-amine (I. N. Zakirov et al., KISI) and polyester urethane (V. S. Minkin et al., K K h T I ) networks and the paramagnetic probe method for the evaluation of segmental mobility of polydiene urea urethanes (L. I. Dashevskii, S. M. K a v u n and A. S. Lykin, NIIShP). Papers were also presented, in which calculations concerning models were compared with the experiment. For example, in a study by R. A. Turusov et al. (ONKhF U.S.S.R. Academy of Sciences) a model of a hollow sphere was used for the study of mechanical effects in frontal solidification of oligomers and an equation was proposed for calculating residual stress in the material. Calculations were made in a paper b y V. P. Roshupkin (OIKhF, U.S.S.R. Academy of Sciences) concerning polymerization stress and structural features and properties of polyesteracrylates, dependent on specific features of thermodynamics of trimerization, analysed. The stage of solidification of polyesteracrylates as a process of the "second gel-point" was examined in a paper by M. P. Berezin and G. V. Korolev (OIKhF, U.S.S.R. Academy of Sciences). A paper b y a large group of authors (E. V. Prut) (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) was concerned with a statistical model of crosslinked polymer structures; this model enabled a quantitative relation to be established between the chemical structure of initial epoxy oligomers, the formation, technical structure and equilibrium physico-mechanical properties of densely crosslinked networks. Papers were read at the final plenary session which were concerned with the various aspects of using oligomers as coatings (L. A. Bakalo et al., IOKh, Ukr.S.S.R. Academy o f Sciences and I K h D , Latv.S.S.R. Academy of Sciences, A. D. Yeselev et al. G I P I LKP), sealants for electrical (S. I. Makarenko et al., KhPI) and constructional (L. M. Demchenko et ~ . , VNIIstroipolimer) purposes, photoconductive films (A. Ya. Veiner et al., N I I O P i K ) , matrices for galvanic copying (R. A. Zakhidov et al., T s P K T B Uzb. S.S.R. Academy of Sciences), printed forms (E. G. Lazarenko et al., Ukrainian Printing Institute), ion-exchange membranes (A. K. Chalov et al., I K h N Kaz.S.S.R. Academy of Sciences), gas-expanded polymers (F. A. Shutov et al., LISI, K. M. Gibov et al., I K h N , Kaz.S.S.R. Academy of Sciences}, glass-fibre reinforced plastics (V. Ye. Bakhareva et al., TsNIITS), etc. A special sectional meeting was concerned with kinetics and the reaction mechanism of oligomers to form linear and crosslinked polymers. Problems of interaction between di-isoeyanates and glycols and triols were dealt with in papers b y S. M. Baturin ~ al. ( O N K h F
I I n d All-Union Conference on Chemistry of Oligomers
"2103
U.S.S.R. Academy of Sciences). Reactions of di-isocyanates with oligotriols a n d oligobutadienodiols wore described in papers b y P. A. Kirpichnikov et al. ( K K h T I ) and Yo. V. Stovbun a n d V. V. Grigor'yeva (O~TKhF U.S.S.R. A c a d e m y of Sciences). Another approach to the formation of crosslinked polyurethanes was described in the paper of L. Yu. R u m y a n t s e v a n d L. I. Golovko (Institute of the Chemistry of High Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences): tri-isocyanate was solidified using alicyclic oligoester. Polymerization of oligourethane acrylates was examined in a paper b y P. V. Datsko and S. S. Gudzer (Institute of the Chemistry of H i g h Molecular Weight Compounds, Ukr.S.S.R A c a d e m y of Sciences}. Specific features of polymerization of oligoester acrylates were examined b y D. A. Aronovich et al. (NIIpolimerov), B. V. Ozerkovskii and V. P. Roshupkina ( O N K h F U.S.S.R. A c a d e m y of Sciences), I. M. Al'shits et ed. (TsNIITS), N. N. Tvorogova a n d I. A. Matveyeva (Institute of Chemical Physics, U.S.S.R. Academy of Sciences}. Solidification of various oligoestermaleate fumarates was examined b y G. P. Zubar' and V. V. Popova (KhPI), Ye. G. Zil'berman et al. (NIIPM). Among papers devoted to network-formation taking place with the opening of epoxy rings greatest attention was a t t r a c t e d b y papers of 0. B. Salamatina et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences}, M. K. P a k t e r et al. (UkrNIIPM), N. K. Moshinskaya et al. (DKhTI), M. F. Sorokina e~ al. (MKhTI), Ye. Ye. Yergozhina, et 02. (IKh!q Kaz.S.S.R. Academy of Sciences), M. F. Sorokina et ed. (MKhTI), Ye. Ye. Yorgozhina et o2. ( I K h N Kaz.S.S.R. A c a d e m y of Sciences) and a series of studies carried out u n d e r the guidance of B. A. Rozenberg (ONKhF, U.S.S.R. Academy of Sciences) and V. N. N i k o l a y e v a (LTI). Papers dealing with the effect of various fields of force on the solidification of oligomers a n d the structure of three-dimensional products formed iV. O. Khozin e$ a/., K I S I ; M. S. Trizno et al., LTI; T. A. K o l ' t s o v a a n d M. S. Akutin, M K h T I , and others) produced livorly discussions. A separate session was devoted to oligomers, the solidification of which produced heat-resistant polymers (oligomers with a conjugated systems and hereto-organic oligomers). A report b y B. 2. Zapadinskii et al. (Institute of Chemical Physics, U.S.S.R. Academy of Sciences) examined results of studying kinetics and the mechanism of formation of oligo(arylenebisbenzimidazoles), their copolymerization with oligoimides and properties of materials based on them. A paper b y Ya. S. Vygodskii et al. (Institute of Hotero-organic Compounds, U.S.S.R. A c a d e m y of Sciences) dealt with crosslinked polymers based on bis-maleimides and cardo-diamines. Various aspects of modification of oligoimides and their polymeri. zation were dealt with in the papers b y G. I. Boiko et al., Zh. Zh. Boyarstanova et al., N . P . Lyubchenko et al. (Institute of Chemical Physics, Kaz.S.S.R. Academy of Sciences); T. S. Tsyganov et al. (Institute of High Molecular Weight Compounds, U.S.S.R. Academy of Sciences); A. I. Mikhal'skii et al. (VIAM); A, I. Volozhin (IFOS, B.S.S.R. A c a d e m y of Sciences) and others. Polyheterearylenes prepared b y isomerizatien ring formation of polycyanurea based on oligomers with aminonitrile end groups and amino-groups were examined b y E. N. Telosheva et al, ( N I F K h I ) , P. M. Valetskii et al. (INEOS U.S.S.R. Academy of Sciences and Moscow Chemico-Teehnological Institute), G. I. Tsvelikhovskii et al. (VNIIEUI), V. K. Skachkova et al., V. A. Grigorovskaya et al. (Institute of Chemical Physics, U.S.S.R. Acad e m y of Sciences} described the structure, properties, special features of network formation of different oligoheteroarylenes a n d materials based on them. New oligomors with t e r n a r y terminal bonds, allene oligomers and oligomors prepared b y motothesis were reported b y A. I. Shorle e$ ag. (Institute of Chemical Physics, U.S.S.R. A c a d e m y of Sciences}, V. A. Bunin et al. ( O I K h F , U.S.S.R. Academy of Sciences). Yu. V. K o r s h a k (INKhS, U.S.S.R. Academy of Sciences).
2104
S. M. M~.ZH~OVSXII and D. B. I z r t ~ o v
Organosilicon compounds were dealt with in most detail of all hetero.organic oligomers. A paper b y I. A. Vostokov and Yu. I. D e r g u n o v (DF GIAP) was concerned with organosilicon earbodi-imide oligomers. Polyorganosiloxanes with peroxidate functional groups were described in a paper b y A. K. Likovets et aL (LPI). A paper b y L. M. Khananashvili ¢t aL (Tbilisi State University) dealt with polyorganosiloxanes with dicyclopentaenyl radicals a t the silicon atom. A paper b y V. P. Misina et al. (Institute of Heteroorganic Compounds, U.S.S.R. A c a d e m y of Sciences) examined the reactivity of carboflmctional oligosiloxanediols in reactions with phenylisocyanate. Three meetings of the section of oligomer and polymer-oligomer mixtures were d o v o t ~ to main problems of thermodynamics of blending, conversion mechanisms and the structure of composites and properties of solidified multi-component materials. There was a lively and fruitful discussion a t the conference concerning the phase condition of polymer-oligomer mixtures. Papers were devoted, in particular, to the free energy variation of mixing b y the sorption method (T. V. Ikanina, et al. Urals State University), determining the Huggins constant b y the method of inversion of gas chromatography (Yu. S. L i p a t o v and A. Ye. Nesterov, IKhVS, Ukr.S.S.R. Academy of Sciences), calculating thermodynamic parameters, results of the microinterference method (a series of studies b y A. Ye. Chalykh carried out jointly b y the I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences and I N K h F , U.S.S.R. Academy of Sciences), thermo-rheological curves (Ye. V. Khabarov, et al. N I I R P ) , deviation from a d d i t i v i t y of optical properties of mixtures (S. A. Yaroshevskii et al., U k r N I I P M ; T. I. R a d b i l ' et al., l~IIpolimerov), evaluating rates of solution (B. S. Grishin et al., N I I S h P and I n s t i t u t e of Chemical Physics, U.S.S.R. A c a d e m y of Sciences), microcalorimetric d a t a (E. F. Wainstein, et al. Institute of Chemical Physics, Ukr.S.S.R. Academy of Sciences) and others. The interpretation of results obtained within the framework of the F l o r y - H u g g i n s , F i e r y - P a t t e r s o n theory and comparison of thermodynamic parameters of the condition of the system with physico-mechanical and technological properties show t h a t the phase condition at different stages of conversion of the multi-component system and regularities of approximation to the equilibrium state is a necessary condition of obtaining materials with given properties. Phase equilibrium was compared in a number of papers with the molecular ar_d supermolecular structure of composites. F o r example, in a paper b y Yu. P. Toms and V. V. Shilov (IKhVS, Ukr.S.S.R. A c a d e m y of Sciences) the structural heterogeneity of oligo-oxymothylene-, ethylene- and propyleneglycol mixtures studied b y wide-angle and small-angle X - r a y diffractometry was compared with thermodynamic parameters of interaction of components. When studying the molecular mobility of polymer-oligomer systems of the oligoesteracryla t e - - p o l y m e r m a t r i x t y p e in the glassy and high-elastic state T. I. Borisova et al. (Institute o f H i g h Molecular Weight Compounds, U.S.S.R. Academy of Sciences and I n s t i t u t e of Chemical Physics, U.S.S.R. Academy of Sciences) differentiated relaxation transitions in connection with the phase equilibrium of the system. The structure of solidified rubber-oligomer compositions was examined b y T. D. Mal'chevskaya et al. (NIIRP), V. S. Derinovskii et aL ( K I S I and O I K h F , U.S.S.R. Academy of Sciences), D. B. Boguslavskii et al. (DF N I I S h P ) , R. Sh. Frenkel' et al. ( V N I K T I R P ) . A s t u d y was made of the effect of the t y p e of oligomer on the structure and proper~iea of polyvinylehloride b y D. B. I z y u m o v et al. (Institute of Chemical Physics, U.S.S.R. Acad e m y of Sciences), P. A. Sukhopar, B. G. Zadontseva et al. (Ukr.NIIPM), M. L. K e r b e r et al. (MKhTI). I m p o r t a n t aspects of the kinetics and mechanism of linear and three-dimensional polymerization of oligomer compounds of different chemical structure were presented b y Yo. V. K h a b a r o v a e t a / . (NIIRP), F. R. Gritsenko (Institute of the Chemistry of High Molecular Weight Compounds, Ukr.S.S.R. A c a d e m y of Sciences), V. F. Popov and V. V. Van'kovieh
I I n d All-Union Conference on Chemistry of Oligomers
2105
(:NIISHP), Yu. R. Ebich et al. (DI~hTI). A paper by T. Ye. Lipatova et al. (IOKh, Ukr.S.S 1~ Academy of Sciences) dealt with the formation of mutually penetrating networks. One of the sectional meetings also examined technical, formulating and other applied aspects of oligomer and polymer-oligomer compounds. Technical and economic problems involved in the production and application of oligomer materials in the n a t i o n a l economy were raised in a special paper b y I. M. Shologon and V. B. Byalykh (UkrNIIPM). I t was noted in the discussion of this paper that technical and economic foundations have not, so far, become widespread enough in oligomer technology. The Conference summarized theoretical and applied problems raised during recent years in the field of oligomers and noted the main trends in subsequent investigations. The resolution passed at the Conference plamled to take a n u m b e r of measures aimed at the speedy introduction of scientific research into the practice of industrial enterprises and at the improvement of training specialists in the field of oligomer technology. I t is planned to hold the I I I r d All-Union Conference on oligomers in Kiev in 1982. Translated by E. SEY~.~RE