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针对聚丙烯酸烷基酯侧基形状、极性的不同,基于高分子链的构象-构型统计理论和生成矩阵方法,推出均方电偶极矩和均方回转半径的改进公式,应用于聚丙烯酸甲酯(PMA)链和聚甲基丙烯酸乙酯(PEMA)链等的链构象依赖性质的研究.得到无规PMA4(4态PMA)和PEMA的偶极矩特征比分别为0.63和0.66,温度系数为-0.66×10-3 K-1和1.72×10-3 K-1,无规PMA和PEMA的均方回转半径的特征比分别为1.73和1.43,温度系数为-1.05×10-3 K-1和-1.28×10-3 K-1,均与实验结果符合.而且考虑链规整程度的不同和酯类基团方向等的改变,PMA和PEMA的特征比也呈现较大的差异,尤其对间同构型链PMA4短链,偶极矩及其温度系数均伴有极大值的出现,这些结果表明聚丙烯酸烷基酯侧基对其链构象性质的影响不能忽略.
Aiming at the different shape and polarity of alkyl polyacrylate side chains, an improved formula of mean square dipole moment and mean square gyration radius was proposed based on the statistical theory of configuration and configuration of polymer chains and the generator matrix method. (PMA) chains and poly (ethyl methacrylate) (PEMA) chains, etc. The characteristic ratios of dipole moment of random PMA4 and PEMA were 0.63 and 0.66 respectively, The temperature coefficients are -0.66 × 10-3 K-1 and 1.72 × 10-3 K-1, the characteristic ratios of mean square radius of gyration of PMA and PEMA are 1.73 and 1.43 respectively, and the temperature coefficient is -1.05 × 10-3 K-1 and -1.28 × 10-3 K-1, respectively, which are in good agreement with the experimental results.And the characteristic ratios of PMA and PEMA also show great differences considering the changes in the degree of chain regularization and the orientation of ester groups, In particular, the short chain, dipole moment and temperature coefficient of the syndiotactic chain PMA4 are accompanied by the occurrence of maximum values. These results indicate that the influence of the side groups of the polyacrylate alkyl on the conformational properties of the chains can not be neglected.