间同1,2-聚丁二烯的结构和结晶动力学研究  

Structure and Non-isothermal Crystallization Kinetics of Syndiotactic 1,2-Polybutadiene

作　　者：卢军[1] 胡雁鸣[2] 张学全[2] 黄葆同[1] 

机构地区：[1]东北大学理学院,辽宁沈阳110004 [2]中国科学院长春应用化学研究所,吉林长春130022

出　　处：《东北大学学报（自然科学版）》2007年第6期909-912,共4页Journal of Northeastern University(Natural Science)

基　　金：国家自然科学基金资助项目(20274046)

摘　　要：间同1,2-聚丁二烯(s-PB)由丁二烯用Fe(2-EHA)3/Al(i-Bu)3/DEP作催化剂,在己烷溶剂中50℃下聚合制备.用13C NMR谱方法测定的1,2-结构含量为89.3%,间同结构为86.5%;X射线测得聚合物的结晶度约为68%.非等温结晶动力学研究采用DSC方法,改进的Avrami方程可以很好地分析s-PB非等温结晶过程的主期结晶,表明其结晶过程是自成核,三维球形生长.Ozawa方程不适合分析s-PB非等温结晶动力学;Avrami和Ozawa方程结合的方法可以很好地描述s-PB非等温结晶过程,指数a为1.138,F(θ)随着结晶度的提高而增大;并计算了s-PB的结晶活化能.Syndiotactic 1,2-polybutadiene（s-PB） was prepared taking Fe（2-EHA）3/Al（i-Bu）3/ DEP as catalyst in hexane at 50 ℃. Characterized by ^13C NMR measurement, the contents of 1,2-structure and syndiotacticity of production are 89.3 % and 86.5 %, respectively, and the crystallinity is about 68%. Differential scanning calorimetry （DSC） was introduced on relevant non-isothermal crystallization kinetics, and the modified Avrami analysis showed that the Avrami exponent varies from 2.73 - 3.22 in primary stage, thus indicating that the crystallization behavior of s-PB is a thermal or athermal self-nucleation growing in three-dimensional spherulization. The Ozawa equation was proved that it fails to describe the non-isothermal crystallization process. However, combining the Avrami and Ozawa equations together can describe the non-isothermal crystallization process well, which shows that the exponent a is 1.138, and F（θ） increases with crystallinity. The effective energy barrier was also calculated.

关 键 词：非等温结晶动力学 间同1 2-聚丁二烯 铁系催化剂 差热扫描 结晶活化能 

分 类 号：O632.12[理学—高分子化学]