摘要
基于改进的旋转异构态模型和生成矩阵统计方法,推导了均方回转半径和均方偶极矩的公式,并应用于研究无机和半无机聚合物构象-构型依赖的性质.计算结果发现,聚合物链的柔性和极性与含杂元素成分、侧基的大小、构象能及链规整程度有关,不对称链比对称链极性更强.聚甲基苯基硅烷(PMPS)和聚二甲基亚硅烷(PDMS)与聚甲基苯基硅醚、聚苯基硅烷和聚磷酸等相比,因侧基高密集分布导致链尺寸较大.尤其是PMPS,其长链在考虑侧基与不考虑侧基影响下计算的链尺寸差异为4. 68%,特性黏数随构型参数和链聚合度增大有较大的变化.同样,PDMS的温度系数随链聚合度增大有独特的变化规律.因此,建议在计算分子链尺寸和极性时,不能忽略侧基的大小、分布和极性.
Formulas of mean-square radius of gyration and mean-square dipole moment were deduced by the improved rotational-isomeric-state model and the generator matrix method.The configuration-conformation{dependent}properties of inorganic and semi-inorganic polymers were investigated by these basic quantities.From comparing the calculated results,it is found that the flexibility and polarity of chain are related to the heteroatom constituents,the size of side group,the conformation energies and tacticity of chain.The polarity of asymmetric polymers is greater than that of symmetric polymers.Duo to existence the crowd side groups,{poly(methylphenylsilylene)(PMPS)}and poly(dimethylsilylene)(PDMS)have greater chain dimensions than those of poly(methlphenysiloxanc),poly(silastyrene)and polyphosphate.Especially,the dimensions of PMPS chain with and without considering side group have a difference of 4.68%.The intrinsic viscosity{changes}obviously as configuration parameters and degree of polymerization increase.Similarly,the{temperature}coefficients of PDMS also change uniquely as degree of polymerization increase.Therefore,it suggests that the size,distribution and polar of side groups cannot be neglected in estimating the dimension and polarity of polymers.
作者
马海珠
韩文韬
陶飞
MA Haizhu;HAN Wentao;TAO Fei(College of Information and Electronic Engineering,Zhejiang Gongshang University,Hangzhou 310018,China)
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2018年第10期2304-2311,共8页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:20904047)
浙江省自然科学基金(批准号:Y17A040005)资助~~
关键词
聚甲基苯基硅烷
聚磷酸
特性率
特性黏数
温度系数
构象
构型
均方回转半径
均方偶极矩
Poly(methylphenylsilylene)
Polyphosphate
Characteristic ratio
Intrinsic viscosity
Temperature coefficient
Configuration
Confromation
Mean-square radius gyration
Mean-square dipole moment
作者简介
马海珠,女,教授,主要从事高分子物理研究.E-mail:mhz@mail.zjgsu.edu.cn.
