Li Chuang, Cui Zefeng, Yang Min, Shi Haifeng, Liu Binyuan
Hebei Key Laboratory of Functional Polymer Materials, School of Chemical Engineering and Science, Hebei University of Technology Tianjin 300130 China
State Key of Separation Membranes and Membrane Process, School of Materials Science and Engineering, Tiangong University Tianjin 300387 China
RSC Adv. 2021 Nov 22;11(59):37317-37324. doi: 10.1039/d1ra07698a. eCollection 2021 Nov 17.
A series of 1-butene/pentafluorophenylundec-1-ene ester random copolymers were synthesized under the Ziegler-Natta catalyst system. The content of the pentafluorophenyl (PFP) group in the copolymer can reach up to 0.59 mol%. The DSC test found that the PFP groups attached to the PB main chain retard the crystalline transformation of Form II to Form I. Nucleophilic aromatic substitutions of pentafluorophenyl ester occurred with biocompatible poly(ethylene glycol) methyl ether (mPEG) introduced into the side chain of PB under very mild conditions. The results show that not only is the crystallization rate of mPEG functionalized PB increased, but also , , and the crystalline phase transition rate of Form II to Form I are also enhanced. Among them, mPEG with a of 500 has the best promoting effect. On the other hand, the hydrophilicity of mPEG-functionalized PB is improved, and it is proportional to the chain length of mPEG. However, the experimental results show that the regularity of the PB structure is the determinant of the rate of crystallization and phase transition.
在齐格勒-纳塔催化剂体系下合成了一系列1-丁烯/五氟苯基十一碳-1-烯酯无规共聚物。共聚物中五氟苯基（PFP）基团的含量可达0.59 mol%。差示扫描量热法（DSC）测试发现，连接在聚丁二烯（PB）主链上的PFP基团阻碍了II型向I型的结晶转变。在非常温和的条件下，将生物相容性聚乙二醇甲醚（mPEG）引入PB侧链，发生了五氟苯基酯的亲核芳香取代反应。结果表明，mPEG功能化的PB不仅结晶速率提高，而且II型向I型的结晶相转变速率也增强。其中，分子量为500的mPEG促进效果最佳。另一方面，mPEG功能化的PB的亲水性得到改善，且与mPEG的链长成比例。然而，实验结果表明，PB结构的规整性是结晶速率和相变速率的决定因素。
