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星形集成橡胶
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    Study on Functionalized Star-shaped Integral Rubber SIBR Copolymer
    氮官能化星形集成橡胶SIBR共聚物的研究
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    The present thesis utilized the N-M-Li as anionic initiator to initiate the butadiene/isoprene/styene system and synthesized nitric functionalized star-shaped integral rubber (N-(SIBR)_n) and solution styrene-butadiene rubber (N-(SSBR)_n). Furthermore, this paper studied systematically the kinetic behavior and heat effect in the polymerization process. The microstructure, molecular weight and its distribution of the copolymers were also investigated in detail.
    采用此引发剂引发苯乙烯、异戊二烯和丁二烯体系,合成了氮官能化星形集成橡胶(N-(SIBR)n)和氮官能化星形溶聚丁苯(N-(SSBR)n),并对其聚合反应过程动力学行为和热效应进行了较为系统的研究,对共聚物的微观结构和分子量及其分布进行了较为深入的研究,同时对共聚物的动态粘弹性、热性能和物理机械性能进行了较为全面的研究。
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A novel star-shaped integrated rubber of butadiene-isoprene-styrene tri-copolymer(SIBR) was prepared in the styrene(St)/isoprene(Ip)/butadiene(Bd) system with self-made N-multi-Li (simplified as Li) as initiator, cyclohexane as solvent and N-N-N′-N′-tetramethylethylenediamine(TMEDA) as polar modifier. The effects of TMEDA/ Li (mole ratio) on polymerization kinetics were investigated. The results showed that each polymerization rate was linear with relative monomer concentration. The reaction rate constant of...

A novel star-shaped integrated rubber of butadiene-isoprene-styrene tri-copolymer(SIBR) was prepared in the styrene(St)/isoprene(Ip)/butadiene(Bd) system with self-made N-multi-Li (simplified as Li) as initiator, cyclohexane as solvent and N-N-N′-N′-tetramethylethylenediamine(TMEDA) as polar modifier. The effects of TMEDA/ Li (mole ratio) on polymerization kinetics were investigated. The results showed that each polymerization rate was linear with relative monomer concentration. The reaction rate constant of Bd firstly increased and then decreased, reaction rate of St increased and reaction rate constant of Ip decreased with increasing TMEDA/Li, respectively. The apparent chain propagation activation energies of Bd, Ip and St were 31.59, 47.64, 31.76 kJ/mol, respectively. The chain growth frequency factors of Bd, Ip and St were respectively 1.02×10~4,1.09×10~6 and 5.27×10~3 min~ -1 when TMEDA/Li was 1.0, divinylbenzene(DVB)/Li(mole ratio) was 0.8 and initiator concentration was 7.69×10~ -4 mol/L.

以自制氮官能化多锂(以下简称Li)为引发剂,N,N,N′,N′-四甲基乙二胺(TMEDA)为极性调节剂,环己烷为溶剂,对苯乙烯(St)、异戊二烯(Ip)、丁二烯(Bd)进行负离子聚合,合成了星形集成橡胶丁二烯-异戊二烯-苯乙烯三元共聚物(SIBR),研究了不同TMEDA/Li(摩尔比)下SIBR的聚合反应动力学。结果表明,在三元共聚合反应中,3种单体的反应速率与其各自浓度均符合一级动力学关系;在SIBR的合成体系中,随着TMEDA/Li的增大,Bd的反应速率常数先升高后降低,St的反应速率常数逐渐增加,Ip的反应速率常数逐渐降低;当TMEDA/Li为1·0、二乙烯基苯(DVB)/Li(摩尔比)为0·8、引发剂浓度为7·69×10-4mol/L时,单体Bd,Ip,St的表观增长反应活化能分别为31·59,47·64,31·76kJ/mol,链增长频率因子分别为1·02×104,1·09×106,5·27×103min-1。

 
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