热可逆黄原酸酯链转移剂制备及在VDF聚合中的应用  

Preparation of Thermoreversible Xanthate Chain Transfer Agent and Its Application in VDF Polymerization

作　　者：翟丛丛 林帅 杨寒 韩吉庆 张坤 张江浩 蔡晨 王鹏 侯学军 刘霞 王威 张亚彬[3] Zhai Congcong;Lin Shuai;Yang Han;Han Jiqing;Zhang Kun;Zhang Jianghao;Cai Chen;Wang Peng;Hou Xuejun;Liu Xia;Wang Wei;Zhang Yabin(Shandong Institute of Non-Metallic Materials,Jinan 250031,China;Quartermaster Energy Quality Supervision Station of Joint Logistic Support Force,Beijing 100071,China;University of Jinan,Jinan 250000,China)

机构地区：[1]山东非金属材料研究所,济南250031 [2]联勤保障部队军需能源质量监督总站,北京100071 [3]济南大学,济南250000

出　　处：《工程塑料应用》2023年第10期160-166,共7页Engineering Plastics Application

基　　金：山东省自然科学基金项目(ZR2022MC154)。

摘　　要：可逆加成-断裂链转移聚合(RAFT)具有聚合物分子量可控且分子量分布较窄的特点,但目前RAFT聚合聚偏氟乙烯(PVDF)调控用链转移剂比较单一。为得到性能更加优异的PVDF基聚合物,采用Diels-Alder反应等方法制备了一种含有动态共价键的新型RAFT聚合用链转移剂,并成功用于偏氟乙烯(VDF)的活性可控聚合。首先,合成得到具有热可逆性质的呋喃保护的马来酰亚胺基黄原酸酯链转移剂(XCTA),通过核磁共振氢谱(1H NMR)确定XCTA的结构。将该XCTA用于VDF的RAFT聚合,经过处理后对聚合物结构以及分子量进行表征和测试,确定得到了含动态共价键的PVDF基聚合物,且XCTA成功实现对VDF的活性调控,得到的PVDF多分散性指数在1.3以下,其远低于普通自由基聚合得到的PVDF。利用XCTA制备的聚合物仍有活性,可继续用于合成性能更加优异的PVDF基嵌段共聚物等,为下一步制备PVDF基多功能聚合物提供了新的思路。Reversible addition-fragmentation chain transfer polymerization(RAFT)has the characteristics of controllable molecular weight and narrow molecular weight distribution of polymer,but currently the chain transfer agent for polyvinylidene fluoride(PVDF)regulation in RAFT polymerization is relatively single.In order to obtain the PVDF-based polymer with more excellent properties,a novel chain transfer agent containing dynamic covalent bonds for RAFT polymerization was prepared by adopting methods such as Diels-Alder reaction and was successfully used for activity-controlled polymerization of VDF.Firstly,xanthate chain transfer agent(XCTA)with thermal reversible furan-protected maleimide was synthesized and the structure of XCTA was determined by proton nuclear magnetic resonance spectroscop(1H NMR).The XCTA was used for RAFT polymerization of VDF.After treatment,the polymer structure and molecular weight were characterized and tested,and a PVDF-based polymer containing dynamic covalent bonds was determined.The activity of VDF was successfully regulated by XCTA.The polydispersity index of PVDF obtained is below 1.3,which is much lower than that obtained by common free radical polymerization.The polymer prepared with XCTA is still active and can be used to synthesize PVDF-based block copolymers with better properties,etc.,which provides a new idea for the next preparation of PVDF-based multifunctional polymers.

关 键 词：聚偏氟乙烯 RAFT聚合 链转移剂 热可逆 

分 类 号：TQ325.4[化学工程—合成树脂塑料工业]