化学学报 ›› 1962, Vol. 28 ›› Issue (5): 267-274.    下一篇

论文

高聚物分级的基本研究——Ⅱ.相分离的溶度函数

应琦琮, 钱人元   

  1. 中国科学院化学研究所
  • 投稿日期:1962-01-30 发布日期:2013-06-03

BASIC STUDIES ON THE FRACTIONATION OF HIGH POLYMERS Ⅱ. ON THE SOLUBILITY FUNCTION OF PHASE SEPARATION

YING CHI-TSUNG, CHIEN JEN-YUAN   

  1. Institute of Chemistry, Academia Sinica
  • Received:1962-01-30 Published:2013-06-03

1.聚甲基丙烯酸甲酯-丙酮-甲醇体系的两次分相实验用θ-溶剂中的沉降速度法测定分相前试样和浓相的分子量分布曲线,得到高分子在浓稀相重量分配的分子量依赖关系
f"j=QeσMj
证实Flory的溶度函数形式与实际相符,并适用于三元体系的相分离,但Q值与两相体积比R值并不相同。2.再分级使级分的分子量分布宽度随再分级次数的增加而减小,通常认为到第三次再分级其效果已不显著并不确实。3.建议一种用两次相分离实验和五次精密的特性粘数测定,结合从[η]和[η]θ值估计分子量分布宽度,得出分子量分布曲线的简便近似力法。

1.The molecular weight dependence of the distribution of polymer molecules between the coacervate and the dilute phases on the phase separation of polymethylmethacrylate-acetone-methanol system has been proved to follow the relation first derived by Flory for binary systems:
f"j=QeσMj
where f"j and f'j are the weight fractions of the polymer molecules of molecular weight Mj in the coacervate and in the dilute phases respectively,while Q andσare parameters.The value of Q found experimentally is not equal to the volume ratio of the two phases as theory for binary systems demands.The molecular weight distributions of the original sample and the coacervate after phase separation were determined by the sedimentation velocity method in a θ-solvent.2.The width of molecular weight distribution of a fraction is found to decrease repeated refractionations.The widely circulated opinion that it is not very effecafter second refractionation is not justified by the present findings.3.A simple approximate method based on the solubility function is suggested for the determination of molecular weight distributions.The method involves only two phase separation experiments and five precise determinations of intrinsic viscosity.