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纸质出版日期:1963-8-20,
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杨焕兴, 韩铁初, 王世敏. 界面缩聚——Ⅱ.聚碳酸酯—影响分子量的主要因素及反应历程的探讨[J]. 高分子学报, 1963,5(1):1-10.
YANG HAUN-SHING, HAN TIEH-CHU, WANG SHIH-MING. INTERFACIAL POLYCONDENSATIONII. POLYCARBONATE--FACTORS AFFECTING THE MOLECULAR WEIGHTOF POLYMER AND A PROPOSED REACTION MACHANISM FOR INTERFACIAL POLYCONDENSATION[J]. Acta Polymerica Sinica, 1963,5(1):1-10.
杨焕兴, 韩铁初, 王世敏. 界面缩聚——Ⅱ.聚碳酸酯—影响分子量的主要因素及反应历程的探讨[J]. 高分子学报, 1963,5(1):1-10. DOI:
YANG HAUN-SHING, HAN TIEH-CHU, WANG SHIH-MING. INTERFACIAL POLYCONDENSATIONII. POLYCARBONATE--FACTORS AFFECTING THE MOLECULAR WEIGHTOF POLYMER AND A PROPOSED REACTION MACHANISM FOR INTERFACIAL POLYCONDENSATION[J]. Acta Polymerica Sinica, 1963,5(1):1-10. DOI:
聚酯合成系界面缩聚中极其重要的方面
但是
对于这类反应的规律性研究
尤其是缩聚过程问题
至今文献尚少。作者以双酚A型聚碳酸酯为对象
系统观察各种因素(催化剂、溶液浓度、碱量、作用物克分子比、溶剂性貭、反应温度等。)对缩聚反应的影响效应
并以此为基础探讨作用过程的历程。实验表明:碱用量系界面缩聚合成聚碳酸酯得以获致高分子量聚合物的主要因素
酰氯及双酚之克分子比对产物分子量具有一定效应
但其影响程度显著弱于平衡缩聚。双酚溶液之浓度变化对聚合物分子量无明显影响
酰氯浓度在一定范围内与产物分子量呈正比关系。与聚酰胺不同
界面缩聚合成聚碳酸酯
无论采用催化剂与否
均要求较长的反应时限
瞬时或数分钟内并不能得到高分子量聚合物。 有机相介貭的正确选择是获致高分子量聚合物的重要因素。作者考核了水相在界面缩聚合成聚酯的反应过程中的功能问题。实验表明
水相中双酚转移入有机相的数量
因反应条件而有所差异。碱用量或双酚与酰氯之克分子比值较高时
部分双酚将始终残留于水相不参加反应
制取高分子量聚酯
并不要求双酚以有节制的速度进入有机相。 在观察各种因素对反应所产生的效应后
作者就界面缩聚合成聚酯历程问题提出了初步见解。
Although the synthesis of polyester is an important branch of interracial polycon-densation,there were only few articles dealing with the reaction behaviours and no con-vincing and decisive conclusions regarding the reaction machanism of interfacial poly-esterification have yet been reached.A systematic study has been made on the influence of various factors (catalysts,duration of reaction,temp.,cone.of reactants,nature of solvent,amount of NaOH used,etc.) upon the interfacial polyesterification of bisphenol-A with phosgen.It has been found that the amount of alkali used in the process was the main factor influencing the molecular weight of the polycarbonate obtained.As one might have expected the effect of molar ratio of initial reactant (phosgen/ bisphenol) on the molecular weight was less important than that in the conventional melt polycondensation.The conc.of bisphenol-A solution had no prominant effect upon molecular weight, while increasing of concentration of phosgen solution favored the growth of molecular weight.Quaternary ammonium salts did asist the polymerization,and in the absence of which,the highest molecular weight was not readily obtained.A major difference between interfacial polyesterification and polyamidation was that in the former case much longer reaction time was required for obtaining high mole- cular weight polymer despite of the presence of quaternary ammonium salt as catalyst.Propor choice of organic solvent was one of the necessary condition for the attain-ment of optimum results.Studies were also made of the function of water phase for interfacial polyesterifica-tion.It has been shown that the quantity of bisphenol reacted with acid chloride varies with the molar ratio of reactants and the amount of alkali used.Regulated transfer of bisphenol across the interface during the course of polyesterification was not the neces-sary condition for preparing polymers with satisfactory molecular weight.According tO the experimental results,the authers proposed a reaction machanism for interfacial polyesterification.
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