POLYMERIZATION OF CONJUGATED DIENES INITIATED BY SOLUBLE ORGANOSODIUM COMPOUNDS IN HYDROCARBON SOLVENTS
POLYMERIZATION OF CONJUGATED DIENES INITIATED BY SOLUBLE ORGANOSODIUM COMPOUNDS IN HYDROCARBON SOLVENTS
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DOI：
10.1002/pi.1995.210370303
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发表时间：
1995-07-01
影响因子：
3.2
通讯作者：
BASOVA, RV
中科院分区：
文献类型：
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作者：
ARESTYAKUBOVICH, AA;PAKURO, NI;BASOVA, RV
研究了非溶剂型有机钠化合物在烃类溶剂中引发丁二烯和异戊二烯的聚合反应。结果表明，聚合物的相对分子质量和MWD主要由向溶剂和聚合物的链转移决定，即使在异戊二烯的情况下也没有观察到向单体的链转移。总聚合速率与单体和引发剂的浓度成正比。丁二烯和异戊二烯在30℃正庚烷中聚合的表观链增长速率常数分别为0.11Lol(-1)S(-1)和0.065 LLmo1(-1)S(-1)。结果表明，聚二烯基钠活性中心的缔合(二聚体)形式在链增长过程中起着重要作用，导致链转移和1，2-丁二烯或3，4-异戊二烯单元含量高于与其他碱金属聚合。
Polymerization of butadiene and isoprene in hydrocarbon solvents initiated by unsolvated organosodium compounds was studied. It was found that the polymer molecular weight and the MWD are determined mainly by chain transfer to solvent and polymer, and no chain transfer to monomer was observed even in the case of isoprene. The overall polymerization rate is proportional to the concentrations of the monomer and the initiator. Apparent chain propagation rate constants were found to be 0.11 litre mol(-1) s(-1) for butadiene and 0.065 litre mol(-1) s(-1) for isoprene polymerization in heptane at 30 degrees C. It is suggested that associated (dimeric) forms of polydienylsodium active centres play an important role in chain propagation, being responsible for a stronger chain transfer and a greater 1,2-butadiene, or 3,4-isoprene, unit content than in polymerization with other alkali metals.