文献类型：期刊文献

中文题名：氯丁橡胶1,2结构单元的中低温异构化转变研究

英文题名：Isomerization transformation of 1,2 structural units in chloroprene rubber

作者：虞远忠[1];夏浙安[1];叶炜[1];孙聪敏[1]

机构：[1]华东理工大学材料科学与工程学院,上海200237

年份：2025

卷号：45

期号：9

起止页码：213

中文期刊名：现代化工

外文期刊名：Modern Chemical Industry

收录：;北大核心:【北大核心2023】；

语种：中文

中文关键词：氯丁橡胶;1;2结构单元;异构化;ZnCl_(2);BPO

外文关键词：chloroprene rubber;1,2 structural units;isomerization;zinc acrylate;benzoyl peroxide

摘要：将牌号为CR^(2)32的氯丁橡胶溶解在甲苯中分别与ZnCl_(2)等助剂在80℃下反应,通过核磁共振氢谱对反应物的结构进行表征分析,发现了1,2结构单元异构化的结构,且胶液未出现交联状态。改变助剂种类和用量、反应气氛、反应时间以及反应温度进行试验研究,结果表明,在80℃时使用ZnCl_(2)(其质量相当于氯丁橡胶质量的0.6%)能够使CR的1,2结构单元在1 h内全部异构化;同样条件下,以丙烯酸锌(ZDA)、CuCl_(2)和Zn(OH)_(2)为助剂时只有较少部分的CR的1,2结构单元发生异构化;以ZnO或MgCl_(2)作助剂时,未发现明显异构化。将反应氛围由氮气改为空气后,异构化过程加快。当反应温度高于60℃时,随温度升高,异构化过程加速。在能发生异构化的体系中加入过氧化苯甲酰(BPO),可提升异构化完成速度,同时也加剧了CR上活性氯的脱出。
CR^(2)32 chloroprene rubber is dissolved in toluene,and reacts with ZnCl2 and other additives at 80℃,the structure of the reactive products is characterized by means of1H-NMR spectroscopy.It is found there is a structural isomerization of 1,2 structural units,and there is not any cross-linking state in rubber solution.The research is conducted through changing the types and amounts of additives,reaction atmosphere,reaction time,and reaction temperature in chloroprene rubber solution.It is found that at 80℃,adding ZnCl2 with an amount as much as 0.6%of CR^(2)32 weight can isomerize all 1,2 structural units of CR^(2)32 within 1 hours.While zinc acrylate(ZDA),CuCl2,and Zn(OH)2 can only isomerize a few of the 1,2 structural units in CR^(2)32 under the same conditions.As ZnO or MgCl2 is served as the additive,no obvious isomerization is observed.The isomerization process will accelerate when the reaction atmosphere changes from nitrogen to air.At a temperature exceeding 60℃,the time required for isomerization declines as the temperature increases.In the system where isomerization can occur,adding benzoyl peroxide accelerates the completion of isomerization and also intensifies the release of active chlorine on CR.