三类引发剂引发苯乙烯聚合特性的比较研究和理论分析  

Study on the Characteristics of the Polymerization of Styrene Initiated by Three Kinds of Initiators

作　　者：黄红军[1] 闫军[1] 张文宇[1] 王行方[1] 

机构地区：[1]军械工程学院理化教研室,石家庄050003

出　　处：《化学通报》2002年第8期549-553,共5页Chemistry

摘　　要：用膨胀计法分别测定了氮 氮键引发剂偶氮二异丁腈 (AIBN)、氧 氧键引发剂过氧化二苯甲酰 (BPO)、碳 碳键引发剂 2 ,3 二氰基 2 ,3 二苯基丁二酸二乙酯的内消旋体 (I)和外消旋体 (II)在苯乙烯中的分解动力学参数 ,分解活化能分别为 :Ed(AIBN) =1 40 0 6kJ·mol-1,Ed(BPO) =1 2 0 3 3kJ·mol-1,Ed(I) =1 0 4 5 2kJ·mol-1,Ed(II) =89 5 6kJ·mol-1;分解活化熵分别为 :ΔS≠(AIBN) =76 3 2J·mol-1·K-1,ΔS≠(BPO) =1 2 76J·mol-1·K-1,ΔS≠(I) =-3 5 2 3J·mol-1·K-1,ΔS≠(II) =-80 84J·mol-1·K-1,并且II的极限转化率α∞ 表现出随温度升高而升高 ,I的α∞ 随温度升高先减小而后趋于平稳的趋势 ,这与AIBN和BPO引发苯乙烯聚合的极限转化率α∞ 随温度的升高而降低的规律有明显不同。对此用动力学链长综合常数k对T的微分结果并结合过渡态理论进行了分析。The kinetics parameter and activation parameter of AIBN、BPO、meso (I) and dl (II) diethyl 2,3 dicyano 2,3 diphenylsuccinate as the initiators were determined in the styrene by dilatometry respectively.The activation energy E d were found to be: E d(AIBN)=140 06kJ·mol -1 , E d(BPO)=120 33kJ·mol -1 , E d(I)=104 52kJ·mol -1 , E d(II)=89 56kJ·mol -1 ,and the activation entropy Δ S NFDA2 ≠ were: Δ S NFDA2 ≠(AIBN)=76 32J·mol -1 ·K -1 , Δ S NFDA2 ≠(BPO)=12 76J·mol -1 ·K -1 , Δ S NFDA2 ≠=-35 23J·mol -1 ·K -1 , Δ S NFDA2 ≠(II)=-80 84J·mol -1 ·K -1 .With the temperature rising,the final conversion α ∞ of II increases gradually,while α ∞ of I diminishes at first,then gradually becomes smooth, and that the final conversion α ∞ both of AIBN and BPO decreases gradually.These phenomena are discussed by the differentiation results of the comprehensive constant k of the kinetic chain length to T .

关 键 词：引发剂 苯乙烯 聚合特性 偶氮二异丁腈 过氧化二苯甲酰 2 3-二氰基-2 3-二苯基丁二酸二乙酯 聚苯乙烯 热分解 

分 类 号：TQ316.3[化学工程—高聚物工业]