聚硅氧烷侧基极性对链均方偶极矩的影响

为了改进无机高分子链偶极矩的计算,在旋转异构态模型和生成矩阵统计方法基础上,导出了可以同时考虑骨架键和侧基极性的均方偶极矩公式,应用于对称和不对称聚硅氧烷高分子链的偶极矩构象构型统计性质的分析,及聚二甲基硅氧烷(PDMS)链、聚甲基苯基硅氧烷(PMPS)链是否考虑侧基极性的偶极矩比较。计算结果表明,PDMS的偶极矩特征比值0.36与实验结果一致,它大于忽略侧基极矩的特征比值约46%,均方偶极矩温度系数为1.29×10-3K-1,无规聚甲基苯基硅氧烷链(50%i-PMPS)的均方偶极矩特征比和温度系数分别为0.61和1.73×10-3K-1.不考虑侧基极性的均方偶极矩特征比与PDMS不考虑侧基时趋于同样的值0.20.对PMPS偶极矩与链规整性关系研究发现,PMPS间同链的均方偶极矩要大于全同和无规链,而全同链温度系数最大.均方偶极矩对一级相互作用能的依赖程度依次按间同链、无规和全同链顺序增加,而间同和全同链均方偶极矩受二级相互作用能的影响要大于无规链.

EFFECT OF SIDE GROUP ORIENTATION ON THE DIPOLE MOMENT OF POLYSILOXANES CHAINS

Basing on the rotational-isomeric-state model and the statistic generator matrix method,the formulas of mean-square dipole moment were deduced in the improved investigation of the disubstituted inorganic polymers,which had considered the dipole moments of both the skeletal bonds and side groups.The revised expression was used to analyze the configurational-conformational dependent dipole moments for the stereoregular and stereoirregular polysiloxane chains,and to compare the mean-square dipole moments of(po...