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用于ε-己内酯与δ-戊内酯均聚和嵌段共聚的二元催化体系。

Binary catalytic system for homo- and block copolymerization of ε-caprolactone with δ-valerolactone.

作者信息

Wang Yan, Han Yongle, Zhang Lifang

机构信息

The Center of Analysis and Test, Shanxi Normal University Linfen 041004 P. R. China.

School of Chemistry & Material Science, Shanxi Normal University Linfen 041004 P. R. China.

出版信息

RSC Adv. 2020 Jul 9;10(43):25979-25987. doi: 10.1039/d0ra04974c. eCollection 2020 Jul 3.

DOI:10.1039/d0ra04974c
PMID:35518598
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9055323/
Abstract

The combined interaction of 2,3,6,7-tetrahydro-5-thiazolo[3,2-] pyrimidine (ITU) as the organocatalytic nucleophile with YCl as Lewis acid cocatalyst, generating ITU/YCl, was employed for homo- and copolymerization of ε-caprolactone (CL) with δ-valerolactone (VL). Poly(caprolactone) (PCL) and poly(caprolactone)-poly(ethylene glycol)-poly(caprolactone) (PCL-PEG-PCL) triblock copolymer and poly(valerolactone)-poly(caprolactone)-poly(ethylene glycol)-poly(caprolactone)-poly(valerolactone) (PVL-PCL-PEG-PCL-PVL) pentablock copolymer were successfully prepared by ring-opening polymerization (ROP) of CL employing ITU/YCl as catalyst in the presence of benzyl alcohol (BnOH) or poly(ethylene glycol) (PEG) as initiator, respectively. The reaction was systematically optimized, and the architecture, molecular weight and thermal properties of the polymers were characterized by NMR, FTIR, SEC and DSC analyses. Finally, a plausible polymerization mechanism was proposed.

摘要

将2,3,6,7-四氢-5-噻唑并[3,2 - ]嘧啶（ITU）作为有机催化亲核试剂与YCl作为路易斯酸共催化剂联合使用，生成ITU/YCl，用于ε-己内酯（CL）与δ-戊内酯（VL）的均聚和共聚反应。分别以苄醇（BnOH）或聚乙二醇（PEG）为引发剂，采用ITU/YCl作为催化剂，通过ε-己内酯的开环聚合（ROP）成功制备了聚己内酯（PCL）、聚己内酯-聚乙二醇-聚己内酯（PCL-PEG-PCL）三嵌段共聚物以及聚戊内酯-聚己内酯-聚乙二醇-聚己内酯-聚戊内酯（PVL-PCL-PEG-PCL-PVL）五嵌段共聚物。对该反应进行了系统优化，并通过核磁共振（NMR）、傅里叶变换红外光谱（FTIR）、尺寸排阻色谱（SEC）和差示扫描量热法（DSC）分析对聚合物的结构、分子量和热性能进行了表征。最后，提出了一种合理的聚合机理。

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