用三异丁基铝/无水磷酸/1,8-重氮-双环[5.4.0]-7-十一碳烯催化体系合成三元氯醚橡胶  

Synthesis of epichlorohydrin rubber with triisobutylaluminum /anhydrous phosphoric acid /1,8-diazo-bicyclo [5. 4. 0]undecene-7 catalytic system

作　　者：赖林海[1,2] 李杨[1] 王玉荣[1] 

机构地区：[1]大连理工大学高分子材料系,辽宁省高分子科学与工程重点实验室,辽宁大连116024 [2]广州恒大材料设备有限公司,广州510620

出　　处：《合成橡胶工业》2015年第3期176-180,共5页China Synthetic Rubber Industry

基　　金：国家自然科学基金重点资助项目(21034001)

摘　　要：以三异丁基铝(简称Al)/磷酸(H3PO4)/1,8-重氮-双环[5.4.0]-7-十一碳烯(DBU)为催化体系、甲苯为溶剂,对环氧氯丙烷(ECH)/环氧乙烷(EO)/烯丙基缩水甘油醚(AGE)进行三元共聚合,考察了催化剂组分及其加料顺序、陈化温度和时间对三元共聚合反应的影响,并对合成的三元氯醚橡胶进行表征。结果表明,在H3PO4中H2O含量为0、H3PO4/Al(摩尔比)为0.35、DBU/Al(摩尔比)为0.5的条件下,采用Al+H3PO4+DBU的加料方式、陈化温度为60℃、陈化时间为2.0 h时,单体转化率可超过97%,所制得的三元氯醚橡胶是由EO、ECH和AGE这3种结构单元组成,当EO/ECH/AGE(摩尔比)为56/40/4时,玻璃化转变温度为-47.2℃。The copolymerization of epichlorohydrin （ECH）, epoxyethane（EO） and allyl glycidyl ether （AGE） was carried out in toluene with Al （i-Bu）3 （simplified as Al ）/H3 PO4/1,8-diazo-bieyclo [ 5. 4. 0 ] undecene-7 （DBU） catalytic system. The effects of the catalyst composition, adding mode of catalyst components, aging temperature and time on poly- merization were investigated, and the synthesized epichlorohydrin rubber was characterized. The re- suits showed that the conversion of monomers reached 97% under the conditions of H2O in H3PO4 0, H3PO4/Al（mole ratio） 0.35, DBU/Al（mole ra- tio） 0.5, aging temperature 60 ℃, aging time 2.0 h and adding mode Al ＋ H3PO4 ＋ DBU. The polymer was composed of EO, ECH and AGE, and the glass transition temperature was - 47.2 ℃ when the mole ratio of EO/ECH/AGE was 56/40/4 .

关 键 词：三异丁基铝 磷酸 1 8-重氮-双环[5.4.0]-7-十一碳烯 环氧氯丙烷 环氧乙烷 烯丙基缩水甘油醚 共聚合 三元氯醚橡胶 

分 类 号：TQ333[化学工程—橡胶工业]