用 ATRA 和 ATRC 进行周期性乙烯基共聚物的合成。

Combination of ATRA and ATRC for the synthesis of periodic vinyl copolymers.

机构信息

Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.

出版信息

Macromol Rapid Commun. 2014 Feb;35(4):474-8. doi: 10.1002/marc.201300721. Epub 2013 Dec 4.

DOI:10.1002/marc.201300721

PMID:24307264

Abstract

A new approach to periodic vinyl copolymers via combination of atom transfer radical addition (ATRA) and atom transfer radical coupling (ATRC) is reported. The two examples are methyl methacrylate (MMA) and styrene (St) periodic copolymer (P(SMMS)) and acrylonitrile (AN) and St periodic copolymer (P(SAAS)). First, two monomer sequence units (MSU) with built-in sequence, SMMS and SAAS, are synthesized through the controlled ATRA of two ATRP initiators with St. Then, the ATRC of SMMS and SAAS are conducted at high radical conditions to generate two types of high-molecular-weight copolymers, P(SMMS) and P(SAAS). Though side reactions can not be totally avoided, characterizations of the polymer structure with a variety of means confirm that the main chain structures of P(SMMS) and (PSAAS) are predominantly with the periodic sequences from the MSUs. Attempts to suppress the side reactions are successful via the MNP-mediated ATRC of SMMS and SAAS.

摘要

本文报道了一种通过原子转移自由基加成（ATRA）和原子转移自由基偶联（ATRC）相结合来制备周期性乙烯基共聚物的新方法。这两个例子是甲基丙烯酸甲酯（MMA）和苯乙烯（St）周期性共聚物（P（SMMS））和丙烯腈（AN）和 St 周期性共聚物（P（SAAS））。首先，通过 St 上的两个 ATRP 引发剂的受控 ATRA 合成了具有内置序列的两个单体序列单元（MSU）SMMS 和 SAAS。然后，在高自由基条件下进行 SMMS 和 SAAS 的 ATRC，生成两种高分子量共聚物 P（SMMS）和 P（SAAS）。尽管无法完全避免副反应，但通过多种手段对聚合物结构进行的表征证实，P（SMMS）和（PSAAS）的主链结构主要来自 MSUs 的周期性序列。通过 SMMS 和 SAAS 的 MNP 介导 ATRC 成功抑制了副反应。