顺丁橡胶的氯化及其氯含量的控制

以次氯酸叔丁酯为氯化剂，氯乙酸为活性氯原子的引入剂，在甲酸存在下合成了既含有活性氯原子又含有惰性氯原子的氯化顺丁橡胶（CBR）。用傅里叶变换红外光谱法、核磁共振法对CBR进行了表征和定量计算。结果表明，CBR的凝胶质量分数低于1％，氯化效率大于90％；氯乙酸既是活性氯原子的引入剂，又是次氯酸叔丁酯的氯离子加成到顺丁橡胶（BR）双键上的促进剂；提高有机酸强度可增加次氯酸叔丁酯对BR的氯化效率；羧基和氯原子是以离子加成机理、等摩尔量加成到BR的双键上，且CBR的惰性氯原子含量和活性氯原子含量可控。

Chlorination of cis-1,4-polybutadiene rubber and control of chlorine content

Chlorinated polybutadiene rubber(CBR) containing active chlorine was synthesized when t-butyl hypochlorite was employed as chlorinating agent under organic acid circumstance(formic acid and chloroacetic acid).CBR was characterized by using infrared spectra and proton nuclear magnetic resonance.The results showed that the chlorination method was of 90% high efficiency and no more than 1% low mass fraction of gel.The chloroacetic acid could not only be used as agent that introduce active chlorine into CBR, but also be used as chlorinating catalyst which made the chlorine atom of t-butyl hypochlorite add into double bonds of BR.The chlorination efficiency increased as the organic acid strength increased.Residual group of organic acid and chlorine were added into double bonds of BR with equal molar ratio,which conformed to ion addition mechanism.