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基于旋转异构态模型和生成矩阵代数方法,重新推导了大侧基聚合物均方回转半径和均方二极矩等基础量公式,应用于对聚乙烯咔唑(PVK)、聚对氯苯乙烯(PPCS)、聚乙烯砒啶(P2VP)和聚乙烯砒咯烷酮(PVP)链构象-构型依赖性质的研究.计算得到其无规链的均方二极矩特征比分别为0.55、0.57、0.48和0.37,均方回转半径特征比分别为2.07、1.74、1.11和1.52,全同链温度系数在?6.1×10?3～2.1×10?3K?1之间,范围比间同和无规链大.比较各特征比变化曲线规律,发现PPCS、PVP和P2VP的基础量分别受聚合物聚合度、规整程度和构象能的影响相对比较明显,而大侧基使PVK的均方二极矩和均方回转半径特征差异显著;对照改进的计算结果表明,在计算均方二极矩和回转半径时考虑极性侧基的方向和尺寸是十分重要的,在聚合物极性和柔性分析中不能忽略极性大侧基的影响.
Based on the rotational isomerism model and the generation matrix algebra method, the fundamental formulas such as the mean square radius of gyration and the mean square dipole moment of large side-chain polymers were deduced and applied to the synthesis of polyvinylcarbazole (PVK), poly-p-chlorobenzene (PPCS), polyvinylpyridine (P2VP) and polyvinylpyrrolidone (PVP) chains, the mean square second-order polarities of the random chains were calculated to be 0.55, 0.57, 0.48 and 0.37, respectively. The mean square radius of gyration features were 2.07, 1.74, 1.11 and 1.52, respectively. The temperature coefficient of the same chain was between 6.1 × 10 -3 and 2.1 × 10 3 K -1, The results showed that the basic amounts of PPCS, PVP and P2VP were relatively affected by the degree of polymerization, the degree of regularity and the conformational energy of the polymer, respectively, while the large side groups made the mean square of PVK Moment and mean square radius of gyration are significantly different. Comparing with the improved calculation results, it is very important to consider the direction and size of the polar side groups in the calculation of the mean square second moment and the radius of gyration. In the polymer polarity and flexibility analysis Can not ignore the influence of large polar side groups.