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Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos

Conference:

Abstract

The synthesis and study of the properties of polymers with conjugated bond systems offers new and extremely promising prospects in the chemistry of high molecular compounds. A high degree of de-localization of p-electrons in the macromolecule is characteristic of such polymer systems. The decrease in the energy excited in the triplet state, just like the diminished ionization potential with large conjugated bonds, conditions the semiconductor and specific magnetic properties of such compounds. In addition, polymer systems with conjugated bonds have proved to be extremely effective stabilizers in the thermo- and photo-oxidation destruction of polymers. The radiation polymerization of acetylene derivatives offers one suitable method of obtaining such polymers and is the only one which ensures that the polymers obtained are free of contamination from initiators at low temperatures. The kinetics of the radiation polymerization of ethynyl benzene and other acetylene derivatives have a number of features typical of ion polymerization quite rare in radical polymerization (speed of polymerization linearly proportional to speed of initiation: very low activation energy; no oxygen inhibition). Nevertheless this polymerization is obviously radical. We reached that conclusion on the basis of a study of polymerization initiation for acetylene hydrocarbons by typical radical initiators - benzoyl peroxide  More>>
Publication Date:
Nov 15, 1963
Product Type:
Conference
Resource Relation:
Conference: Conference on the Application of Large Radiation Sources in Industry, Salzburg (Austria), 27-31 May 1963; Other Information: 6 figs., 3 tabs., 10 refs.; Related Information: In: Industrial Use of Large Radiation Sources. Proceedings of a Conference on the Application of Large Radiation Sources in Industry. V. I| 436 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETYLENE; ACTIVATION ENERGY; BENZENE; BENZOYL PEROXIDE; CONTAMINATION; COPOLYMERIZATION; COPOLYMERS; DECOMPOSITION; KINETICS; MAGNETIC PROPERTIES; MIXTURES; OXIDATION; RADICALS; SEMICONDUCTOR MATERIALS; SYNTHESIS; VINYL MONOMERS
OSTI ID:
22100754
Research Organizations:
International Atomic Energy Agency, Vienna (Austria)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13R0330058802
Submitting Site:
INIS
Size:
page(s) 151-164
Announcement Date:
Jun 06, 2013

Conference:

Citation Formats

Barkalov, I. M., Gol'danskij, V. I., and Go, Min'-Gao. Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos. IAEA: N. p., 1963. Web.
Barkalov, I. M., Gol'danskij, V. I., & Go, Min'-Gao. Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos. IAEA.
Barkalov, I. M., Gol'danskij, V. I., and Go, Min'-Gao. 1963. "Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos." IAEA.
@misc{etde_22100754,
title = {Radiation Polymerization of Acetylene Hydrocarbons. Special Features; Particularites de la polymerisation radiochimique des hydrocarbures acetyleniques; Radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh; Particularidades de la radiopolimerizacion de los hidrocarburos acetilenicos}
author = {Barkalov, I. M., Gol'danskij, V. I., and Go, Min'-Gao}
abstractNote = {The synthesis and study of the properties of polymers with conjugated bond systems offers new and extremely promising prospects in the chemistry of high molecular compounds. A high degree of de-localization of p-electrons in the macromolecule is characteristic of such polymer systems. The decrease in the energy excited in the triplet state, just like the diminished ionization potential with large conjugated bonds, conditions the semiconductor and specific magnetic properties of such compounds. In addition, polymer systems with conjugated bonds have proved to be extremely effective stabilizers in the thermo- and photo-oxidation destruction of polymers. The radiation polymerization of acetylene derivatives offers one suitable method of obtaining such polymers and is the only one which ensures that the polymers obtained are free of contamination from initiators at low temperatures. The kinetics of the radiation polymerization of ethynyl benzene and other acetylene derivatives have a number of features typical of ion polymerization quite rare in radical polymerization (speed of polymerization linearly proportional to speed of initiation: very low activation energy; no oxygen inhibition). Nevertheless this polymerization is obviously radical. We reached that conclusion on the basis of a study of polymerization initiation for acetylene hydrocarbons by typical radical initiators - benzoyl peroxide and the dinitrile of azoisobutyric acid. They investigated the kinetic features and mechanism of peroxide decomposition in the presence of acetylene hydrocarbons (e.g. ethynyl benzene, deutero-ethynyl benzene and phenylpropyne). The kinetics of radiation co-polymerization of ethynyl benzene with different vinyl monomers and the composition of copolymers in different initial mixtures were also studied. These data and the results of a study of the kinetics of inhibited ethynyl benzene polymerization (benzoquinone initiator) indicate a small reactivity capacity of the ethynyl benzene radical. The pronounced deviations from the additivity rule in the case of radiation polymerization in different solvents indicate a large energy transfer to acetylene hydrocarbons and their polymers. (author) [French] La synthese des polymeres a systeme reticule et l'etude de leurs proprietes constituent une branche nouvelle et tres riche en promesses de la chimie des composes a poids moleculaire eleve. Les polymeres de ce type sont caracterises par un haut degre de deplacement des electrons p dans la macromolecule. La reduction de l'energie d'excitation jusqu'a formation de la triple liaison et la diminution du potentiel d'ionisation en presence de longues chafhes de reticulation sont a l'origine des proprietes semi-conductrices et des particularites magnetiques specifiques de ces composes. En outre, ces systemes reticules se sont reveles tres efficaces comme stabilisateurs contre la destruction des polymeres par thermo-oxydation et photo-oxydation. Une methode pratique pour obtenir des polymeres de ce genre est fournie par la polymerisation radiochimique des derives de l'acetylene. Elle seule permet d'obtenir, a basse temperature, des polymeres libres de toute impurete due aux initiateurs. La cinetique de la polymerisation radiochimique du phenylacetylene et d'autres derives de l'acetylene presente une serie de traits qui sont caracteristiques de la polymerisation ionique mais tout a fait inhabituels pour la polymerisation par radicaux (vitesse de polymerisation preportionnelle a la vitesse d'amorcage; energie d'activation tres faible; absence d'inhibition par l'oxygene). Neanmoins, cette polymerisation semble etre due a l'action des radicaux. Les auteurs sont parvenus a cene conclusion, en etudiant l'amorcage de la polymerisation des hydrocarbures acetyleniques par des initiateurs ayant le caractere typique d'un radical, tel que le peroxyde de benzoide et le dinitryle de l'acide azo-i-butyrique. A ce propos, ils ont examine les particularites de la cinetique et du mecanisme de la degradation du peroxyde en presence d'hydrocarbures acetyleniques (notamment de phenylacetylene, de deuterophenylacetylene et de methylphenylacetylene). Les recherches ont egalement porte sur la cinetique de la copolymerisation radiochimique du phenylacetylene avec divers monomeres vinyliques et sur la composition des copolymeres formes a partir de melanges divers. Ces donnees ainsi que les resultats obtenus en etudiant la cinetique de la polymerisation inhibee du phenylacetylene (l'inhibiteur etait le benzoquinone) montrent que le radical du phenylacetylene reagit faiblement. Les ecarts sensibles de la regle d'additivite constates lors d e la polymerisation radiochimique dans divers solvants temoignent d'un important transfert d'energie vers les hydrocarbures acetyleniques et leurs polymeres. (author) [Spanish] La sintesis y el estudio de las propiedades de los polimeros con enlaces conjugados ofrecen nuevas peispectivas a la quimica de los compuestos de elevado peso molecular. Una caracteristica de los polimeros de ese tipo es el alto grado de desplazamiento de los electrones p en la macromolecula. La reduccion de la energia de excitacion hasta la formacion del triple enlace, asi como la disminucion del potencial de ionizacion en presencia de las largas cadenas reticuladas, dan lugar a propiedades semiconductoras y magneticas especificas en esos compuestos. Ademas, se comprueba que estos compuestos con enlaces conjugados son estabilizadores muy eficaces en la termooxidacion y fotooxidacion destructiva de los polimeros. Un metodo conveniente de obtencion de esos polimeros es la radiopolimerizacion de los compuestos acetilenicos. Constituye la unica forma de obtenerlos exentos de impurezas (iniciadores) a bajas temperaturas. La cinetica de la radiopolimerizacion del fenilacetileno y otros compuestos acetilenicos presenta una serie de rasgos que son caracteristicos de la polimerizacion ionica, pero que resultan totalmente excepcionales en el caso de la polimerizacion por radicales (v.g., velocidad de polimerizacion proporcional a la velocidad de iniciacion; energia de activacion muy pequefla; ausencia de inhibicion por el oxigeno). Sin embargo, se trata indudablemente de una polimerizacion por radicales. Los autores llegaron a esa conclusion al estudiar la iniciacion de la polimerizacion de hidrocarburos acetilenicos por compuestos que poseen caracteristicas de radicales, a saber, el peroxido de benzoilo y el dinitrilo del acido azoisobutirico. Estudiaron asi las propiedades cineticas y el mecanismo de degradacion del peroxido en presencia de hidrocarburos acetilenicos (v.g., fenilacetileno, deuterofenilacetileno y metilfenilacetileno). Tambien investigaron la cinetica de la copolimerizacion del fenilacetileno con diferentes monomeros vinilicos y la composicion de los copolimeros producidos a partir de distintas mezclas iniciales. Estos datos, juntamente con los resultados del estudio de la cinetica de la polimerizacion del fenilacetileno (usando benzoquinona como inhibidor) demuestran la escasa capacidad de reaccion del radical fenilacetilenico. La marcada desviacion con respecto a la ley de aditividad observada en la radiopolimerizacion en diversos disolventes, es indice de una considerable transferencia de energia a los hidrocarburos acetilenicos y sus polimeros. (author) [Russian] Sintez i issledovanie svojstv polimerov s sistemoj sopryazhennykh svyazej yavlyaetsya novym i ves'ma perspektivnym napravleniem v khimii vysokomolekulyarnykh soedinenij. Kharakternoj chertoj takikh polimernykh sistem yavlyaetsya bol'shaya stepen' delokalizatsii P-ehlektronov v makromolekule. Umen'shenie ehnergii vozbuzhdeniya v trepletnoe sostoyanie, ravno kak i ponizhenie potentsiala ionizatsii pri bol'shikh tsepyakh sopryazheniya, obuslavlivaet poluprovodnikovye i spetsificheskie magnitnye svojstva ehtikh soedinenij. Krome togo, ehti polimernye sistemy s sopryazhennymi svyazyami okazalis' ves'ma ehffektivnymi stabilizatorami termo- i fotookislitel'noj destruktsii polimerov. Udobnym sposobom polucheniya podobnykh polimerov yavlyaetsya radiatsionnaya polimerizatsiya atsetilenovykh proizvodnykh. Tol'ko ehtot sposob obespechivaet poluchenie polimerov, svobodnykh ot zagryazneniya initsiatorami pri nizkikh temperaturakh. Kinetika radiatsionnoj polimerizatsii fenilatsetilena i drugikh atsetilenovykh proizvodnykh imeet ryad osobennostej, kharakternykh dlya ionnoj polimerizatsii, no sovershenno neobychnykh dlya radikal'noj (skorost' polimerizatsii proportsional'na pervoj stepeni skorosti initsiirovaniya; ehnergiya aktivatsii ochen' mala; ket ingibirovaniya kislorodom). Tem ne menee ehta polimerizatsiya yavlyaetsya, vidimo, radikal'noj. K takomu vyvodu my prishli na osnove issledovaniya initsiirovaniya polimerizatsii atsetilenovykh uglevodorodov tipichno radikal'nymi initsiatorami - perekis'yu benzoila i dinitrilom azoizomaslyanoj kisloty. V ehtoj svyazi izuchalis' osobennosti kinetiki i mekhanizma raspada perekisi v prisutstvii atsetilenovykh uglevodorodov (naprimer, fenilatsetilena, dejtero-fenilatsetilena i metilfenilatsetilena). Izuchalis' takzhe kinetika radiatsionnoj sopolimerizatsii fenilatsetilena s razlichnymi vinilovymi monomerami i sostav sopolimerov pri razlichnykh iskhodnykh smesyakh. EHti dannye, a takzhe rezul'taty izucheniya kinetiki ingibirovannoj polimerizatsii fenilatsetilena (ingibitor - benzokhinon) ukazyvayut na maluyu reaktsionnuyu spooobnost' fenilatsetilenovogo radikala. Sil'nye otkloneniya ot pravila additivnosti pri radiatsionnoj polimerizatsii v razlichnykh rastvoritelyakh svidetel'stvuyut o nalichii sil'nogo perenosa ehnergii k atsetilenovym uglevodorodam i ikh polimeram. (author)}
place = {IAEA}
year = {1963}
month = {Nov}
}