通过正离子聚合淤浆法,以异丁烯和对甲基苯乙烯为原料、二氯乙基铝/2-氯-2,4,4-三甲基戊烷(AlEtCl2/TMPCl)为引发体系,制备了无规共聚物,并使用自由基引发剂偶氮二异庚腈(AVBN)在55℃遮光条件下进行溴化得到主链结构全饱和的溴化聚(异丁烯-co-对甲基苯乙烯)无规共聚物(BIMS),使用四甲基乙二胺(TEMED)与自制的可逆硫化剂双环戊二烯二甲酸钾盐[DCPD(COOK)₂]进行硫化加工。结果表明:在-86℃下进行反应,AlEtCl₂与TMPCl摩尔比为18时,稳定性及重复性较好,其分子量达到24kg/mol;自由基引发剂AVBN质量含量在0.75×10^-3%时,溴化反应效果较好;DCPD(COOK)₂与TEMED相比具有更好的效果,二次硫化加工时拉伸强度平均下降10.6%,断裂伸长率平均下降16.5%,在添加5份DCPD(COOK)₂时拉伸强度最大,达到4.9MPa,具有较好的再加工性。

Random copolymers were prepared by cationic polymerization slurry method with isobutylene and p-methylstyrene as raw materials and AlEtCl₂/TMPCl as initiator.The free radical initiator AVBN was brominated under the shading condition of 55℃ to obtain brominated poly (isobutene-co-p-methylstyrene) random copolymer (BIMS) with fully saturated main chain structure.Tetramethylethylenediamine (TEMED) and potassium dicyclopentadienyl dicarboxylate [DCPD(COOK)₂],a self-made reversible vulcanizing agent,were used for vulcanization.The results showed that when the molar ratio of AlEtCl₂ to TMPCl was 18,the stability and repeatability of the reaction were good,and the molecular weight reached 24kg/mol.When the dosage of free radical initiator AVBN was 0.75×10^-3wt%,the effect of bromination reaction was better.Compared with TEMED,DCPD(COOK)₂ had better effect.The average tensile strength and elongation at break decrease by 10.6% and 16.5% during secondary vulcanization.When adding 5phr DCPD(COOK)₂,the tensile strength reached 4.9MPa,which had better reprocessability.