SnLi引发苯乙烯/异戊二烯/丁二烯聚合动力学

Polymerization Kinetics Behavior of Butadiene/Isoprene/Styrene with Tin-Containing Organolithium as Initiator

以含锡有机锂(SnLi)为引发剂,四氢呋喃(THF)为结构调节剂,环己烷为溶剂,对苯乙烯(St)、异戊二烯(Ip)和丁二烯(Bd)进行阴离子聚合,合成了锡官能化St-Ip-Bd三元共聚物(SIBR),研究了不同THF/SnLi(摩尔比)和引发温度下的聚合动力学。结果表明,在三元共聚合中,三种单体的反应速率与其各自浓度均符合一级动力学关系;随着引发温度的升高和THF/SnLi的增大,各单体的反应速率常数逐渐增大;当THF/SnLi为30时,单体BdI、p、St的表观增长反应活化能分别为68.486 kJ/mol,87.984 kJ/mol,76.351 kJ/mol,链增长频率因子分别为2.86×1010min-1,1.47×1013min-1,3.40×1011min-1。

A novel tin-functionalized integrated rubber of butadiene-isoprene-styrene tri-copolymer （SIBR） for high performance tire tread was prepared with self-made tin-containing organolithium （SnLi） as initiator, cyclohexane as solvent and tetrahydrofuran （TIqF） as polar modifier. The effects of THF/SnLi （mole ratio） and initiation temperature on polymerization kinetics were investigated. The results show that polymerization rate is linear with relative monomer concentration. The reaction rate constant of each monomer increases gradually with increasing THF/SnLi and temperature. The apparent chain propagation activation energies of Bd, Ip and St is 68.486 kJ/mol, 87.984 kJ/mol, 76.351 kJ/mol, respectively. The chain growth frequency factors of Bd, Ip and St is respectively 2.86 × 10^10 min^-1 , 1.47 × 10^13 min^- 1 and 3.40 × 10^11 min^-1 when the content ratio of THF/SnLi is 30.