Preparation and Polymerization of Unsaturated Quaternary Ammonium Compounds. V. Propargyl Derivatives1
Preparation and Polymerization of Unsaturated Quaternary Ammonium Compounds. V. Propargyl Derivatives1
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不饱和季铵化合物的制备和聚合。
DOI：
10.1021/ja01632a022
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发表时间：
1954
影响因子：
15
通讯作者：
Roger A. Johnson
中科院分区：
文献类型：
--
作者：
G. Butler;Roger A. Johnson
为了确定具有丙炔基作为一个或多个取代基的季铵化合物是否会以类似于相应的烯丙基衍生物的方式进行自由基催化聚合，制备并表征了许多含有该基团的化合物。该系列化合物的不饱和基团为：一个丙炔基、一个丙炔基和一个烯丙基、一个丙炔基和两个烯丙基、一个丙炔基和三个烯丙基、两个丙炔基和一个烯丙基。作为这些化合物的中间体，制备了四种不饱和叔胺并对其进行了表征。聚合研究表明，只有那些含有两个或两个以上烯丙基的化合物才会产生聚合物，而丙炔基不会参与聚合。先前的工作2-3表明含有两个或两个以上烯丙基或氯烯丙基的不饱和季铵盐通过自由基催化机制进行聚合。最近的研究表明，尽管乙烯醚可以通过自由基催化机制与各种烯烃化合物共聚，但当存在季铵盐时，这些基团不能与任何可能存在的烯丙基聚合或共聚。虽然资料尚不充分，不能对乙炔化合物的聚合和共聚进行广泛的概括，但已经发现许多这类化合物都能发生这些反应。乙烯乙炔在压力下，有或没有通常的催化剂，如过氧化苯甲酰或硼酸钠，很容易通过加热聚合形成粘性干燥油，最后形成坚硬的树脂固体。雅各布斯和惠特彻已经证明，苯氧乙炔发生聚合，通常是剧烈的聚合。Ladd6表明，在自由基形成催化剂的存在下，丙炔乙酸酯与溴三氯甲烷发生自由基引发反应，生成2-溴- 4,4,4 -三氯-2-丁烯乙酸酯。Bruson和butler已经证明了2-硝基-2-
In order to determine whether or not quaternary ammonium compounds having the propargyl group as one or more of the substituents would undergo a free radical catalyzed polymerization in a manner similar to the corresponding allyl derivatives, a number of compounds containing this group were prepared and characterized. This series consisted ofcompounds con-taining, as the only unsaturated groups, one propargyl group, one propargyl and one allyl group, one propargyl and two allyl groups, one propargyl and three allyl groups, and two propargyl and one allyl groups. As intermediatesfor these com-pounds, four unsaturated tertiary amines were prepared and characterized. Polymerization studies showed that only those compounds containing two or more allyl groups producedpolymers, and that the propargyl groups did not enter into the polymerization.Previous work2-3 has shown that unsaturated quaternary ammonium salts containing two or more allyl or chloroallyl groups undergo polymerization by a free radical catalyzed mechanism. More re-cent work4 has shown that even though vinyl ethers will copolymerize with a variety of olefinic com-pounds by a free radical catalyzed mechanism, such groups, when present inquaternary ammonium salts, do not polymerize or copolymerize with any allyl groups which may be present. Although data are as yet insufficient to permit wide generalizations with regard to polymerization and copolymerization of acetylenic compounds, many compounds of this type have been found to undergo these reactions. Vinylacetylene under pressure, with or without the usual catalysts such as benzoyl peroxide or sodium borate, is readily polymerized by heat to form viscous drying oils and finally hard resinous solids. Jacobs and Whitcher6 have shown that phenoxyacetvlene undergoes polymerization, quite often violently. Propargyl ace-tate has been shown by Ladd6 to undergo a free radical initiated reaction with bromotrichlorometh-ane in presence of free radical forming catalysts to give 2-bromo-4, 4, 4-trichloro-2-butenyl acetate. Bruson and Butler7 have shown that 2-nitro-2-