374. Liquid-phase reactions at high pressures. Part II. The polymerisation of olefins
374. Liquid-phase reactions at high pressures. Part II. The polymerisation of olefins
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374. 高压下的液相反应。
DOI：
10.1039/jr9370001784
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发表时间：
1937
期刊：
影响因子：
--
通讯作者：
D. Newitt
中科院分区：
文献类型：
--
作者：
R. Sapiro;R. Linstead;D. Newitt
在催化剂存在下形成的聚合物，通过在较高温度下的压力聚合获得。低级聚合物的形成遵循与高级聚合不同的过程，并且高级聚合物不能通过对α-甲基苯乙烯的不饱和二聚体施加高压来制备。在所研究的物质中，只有ArylCRXH类型的化合物才能实现高度聚合。当有机分子聚合时，它们通常会产生稳定性更高（在合理的低温下）和分子体积更小的物质。因此，该反应是一种预期会受到压力增加的促进的反应。Conant和Tongberg（J. Anzer.化学SOC.，1930，52，1659）观察到异戊二烯在12，000atm下容易聚合。在室温下的压力，以及Tammann和Pape（2. anorg.克莱姆，1931，200，113）指出，压力高达3000大气压。对烯烃聚合的影响比他们研究的其他液相反应更大。高压作为实现聚合的手段的一个特别的优点是它可以在相对温和的条件下引起反应，从而减少高温和剧烈催化剂的干扰影响。本文叙述了在10，000大气压以下，对某些取代乙烯，特别是α-甲基苯乙烯的聚合进行的探索性工作，并且在100-ca. 160 "。
formed in the presence of catalysts, are obtained by pressure polymerisation at higher temperatures. The formation of the lower polymers follows a different course from the high polymerisation, and high polymers cannot be made by the application of high pressure to the unsaturated dimer of a-methylstyrene. High polymerisation among the substances studied is only realised in compounds of the type ArylCRXH,.WHEN organic molecules polymerise they normally do so to yield substances of greater stability (at reasonably low temperatures) and lower molecular volume. Hence the reaction is one which would be expected to be favoured by increase in pressure. Conant and Tongberg (J. Anzer. Chem. SOC., 1930, 52, 1659) observed the ready polymerisation of isoprene under 12,000 atm. pressure at room temperature, and Tammann and Pape (2. anorg. Clzem., 1931, 200, 113) noted that pressures up to 3000 atm. had a greater influence on the polymerisation of olefins than on the other liquid-phase reactions studied by them. A particular advantage of high pressure as a means of effecting polymerisation is that it may bring about reaction under comparatively mild conditions, and thereby diminish disturbing influences of high temperatures and drastic catalysts. The present paper deals with explorative work on the polymerisation of some substituted ethylenes, and particularly of a-methylstyrene, at pressures up to 10,000 atm., and at temperatures of 100-ca. 160".