文章摘要
以2,2-二(5-甲基-2-四氢呋喃基)丙烷为极性调节剂合成苯乙烯/异戊二烯/丁二烯聚合动力学
Polymerization Kinetics Behavior of Styrene/Isoprene/Butadiene Terpolymer with 2,2-Bis(5-Methyl-2-Oxolanyl)Propane as Polar Modifier
  
DOI:10.16865/j.cnki.1000-7555.2018.05.003
中文关键词: 苯乙烯-异戊二烯-丁二烯三元共聚物  2,2-二(5-甲基-2-四氢呋喃基)丙烷  四氢呋喃  阴离子聚合  聚合动力学
英文关键词: styrene-isoprene-butadiene terpolymer  2,2-bis[(5-methyl-2-oxolanyl)]propane  tetrahydrofuran  anionic polymerization  polymerization kinetics
基金项目:中国石油化工股份有限公司科研项目(214014)
作者单位
康新贺1,2, 刘淑琴1, 王 雪2, 徐 林2, 李传清2 1. 中国矿业大学(北京) 化学与环境工程学院北京 1000832. 中国石化北京北化院燕山分院 橡塑新型材料合成国家工程研究中心北京 102500 
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中文摘要:
      以正丁基锂(n-BuLi)为引发剂,2,2-二(5-甲基-2-四氢呋喃基)丙烷(DMOP)为极性调节剂,采用阴离子聚合法合成苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物(SIBR),研究了不同DMOP/n-BuLi(摩尔比)和不同反应温度条件下的三元共聚合反应动力学及共聚物的微观结构,并与极性调节剂四氢呋喃(THF)进行了比较。结果表明,在单体质量分数为12%,St/Ip/Bd(质量比)为22/38/40,设计单臂相对分子质量为12×104的条件下,3种单体的聚合反应速率与单体浓度之间呈线性关系,随着DMOP/n-BuLi(摩尔比)的增大或聚合反应温度的升高,各单体聚合反应速率逐渐增大,聚合反应的假一级表观增长反应速率常数增大;当DMOP/n-BuLi为1.0时,3种单体St,Ip,Bd的Ea″分别为71.868 kJ/mol,53.553 kJ/mol,71.403 kJ/mol,频率因子分别为6.61×1010 min-1,5.68×107 min-1,7.88×1010 min-1;随着DMOP与n-BuLi摩尔比的增大或聚合反应温度的降低,共聚物中总1,2-结构含量和Ip3,4含量明显增加,而Bd1,4和Ip1,4结构含量明显减少;DMOP在用量较小的情况下其效果优于较大THF用量的情况,促进聚合反应速率的能力明显高于THF。
英文摘要:
      Styrene-isoprene-butadiene terpolymer(SIBR)was synthesized with n-BuLi as initiator,2,2-bis[(5-methyl-2-oxolanyl)]propane(DMOP) as polar modifier by anionic polymerization. The effects of n(DMOP)/n(n-BuLi)and polymerization temperature on copolymerization kinetics were investigated,the microstructures of SIBR were analyzed, and the comparison was conducted with system of tetrahydrofuran(THF)as polar modifier. The results show that under the conditions of mass fraction of monomer is 12%,mass ratio of St/Ip/Bd is 22/38/40,relative molecular weight is 12×104,the polymerization rate of St, Ip and Bd is linear with monomer concentration,the polymerization rate of St, Ip and Bd and the apparent propagation reaction rate constants (Kp″) increase gradually with the increase of mole ratio of DTHFP/Li and the rise of polymerization temperature. When the mole ratio of DMOP/Li is 1.0,the apparent chain propagation activation energies of St, Ip and Bd is 71.868 kJ/mol, 53.553 kJ/mol, 71.403 kJ/mol, respectively. The freauency factors of St, Ip and Bd is 6.61×1010 min-1,5.68×107 min-1,7.88×1010 min-1, respectively. With the increase of mole ratio of DMOP to n-butyl lithium or the decrease of polymerization temperature,the content of total 1,2-structure and Ip3,4 increases dramatically,the content of Bd1,4 and Ip1,4 decreases clearly. When using a small amount of DMOP,the effect is better than that of using a large amount of THF,the ability of improving the polymerization rate of DMOP is much more effective than that of THF.
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