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纸质出版日期:1964-6-20,
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毕先同, 王葆仁. 己内酰胺的聚合——Ⅳ.一元羧酸对聚合过程所发生的作用[J]. 高分子学报, 1964,6(3):171-177.
PI HSIEN-TUNG, WANG PAD-JEN. THE POLYMERIZATION OF CAPROLACTAM——Ⅳ. THE R6LE PLAYED BY THE MONOBASIC CARBOXYLIC ACID DURING THE COURSE OF POLYMERIZATION[J]. Acta Polymerica Sinica, 1964,6(3):171-177.
己内酰胺在苯甲酸和6-氨基己酸存在下的聚合反应
实验结果表明苯甲酸具有引发 单体聚合、酸解大分子链和酰化大分子的氨基的作用。反应的开始为催化引发单体生成大分子链而不是苯甲酸与单体的加成。随着大分子的增多
酸解和酰化也同时发生。在反应半小时后酸解的影响逐渐显著
到3—4小时以后
酸解影响超过缩聚使聚合物分子量下降羧基含量增加。到反应7—8小时后
聚合物生成量及分子量已达恒定而酰化仍继续进行。到反应达到平衡时
仍然有游离的苯甲酸
聚合物中仍有游离的氨基和羧基
说明酸解、酰化与缩聚都是可逆反应。 在不用苯甲酸的己内酰胺与水的聚合实验中
聚合物虽在常压通氮的情况下在250°
270°或300°加热6小时分子量仍能稳定在一定数值而不升高
即加热15小时(250°)变化也很小。氨基与羧基不再进行缩聚
可能系由于反应系统粘稠
水分子不易扩散除去
大分子不易移动接触
功能基又受本身分子链的空间阻碍
使反应不易继续进行
维持在一定平衡状态。
In the polymerization of caprolactam in presence of 6一amino—caproic acid and benzoic acid.experimental results indicated that the r61e played by the benzoic acid in-cluded:the formation of polymer chains by“induction”,the acid—splitting reaction of the macromolecular chains and the acylation reaction of the amino-group of the macro-molecules.During the beginning stage of the reaction,benzoic acid exerted a catalytic action on the monomer molecules causing them to unite to macromolecular chains and did not add to the monomer.As the reaction was going on,when the number of macromole-cules gradually increased,acid splitting reaction became more and more pronounced;and,after 3—4 hours’ reaction, it surpassed p01ycondensation and made the molecular weight of the polymer decreased and the carboxyl.content increased.The acylation reaction was clearly indicated after 7—8 hours’reaction when the quantity of the polymer formed and the molecular weight of the polymer have already reached constant values,while the consumption of the benzoic acid was still going on.At the end of the reaction.when the ultimate equilibrium has been established,there was still found free benzoic acid and free carboxyl-groups;this indicated that acid-splitting, acylation and polycondensation are all reversible reactions.In the experiments on the polymerization of caprolactam in presense of water but in absense of carboxylic acid,the polymers obtained was heated'at 250°。270°or at 300°under ordinary pressure while a stream of nitrogen was passed through.The molecular weight of the polymer did not increase after heated for 6 hours (and in case of 250°,for 15 hours).The reason for no further condensation might be that the reaction medium became highly viscous which prevented the escape of water molecules and made the dif-fusion and collision of the macromolecules difficult. At the sametime,the steric hinde-rance of the macromolecular chain exerted on the functional groups became more and more pronounced when the chain reached certain definite 1ength.These all made the polycondensation stopped at a certain stage.
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