Azide-Capped Poly(alkoxycarbonylmethylene)s for Click Chemistry: Their Syntheses by 2-Bromoethanol-Mediated Chain Transfer Polymerization of Diazoacetate Followed by Azidation

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-16 DOI:10.1021/acs.macromol.6c01954

Hiroaki Shimomoto,Momoe Kawata,Yusuke Kuzukawa,Rika Okawaki,Kaori Miyahara,Tomomichi Itoh,Eiji Ihara

引用次数: 0

Abstract

Abstract An effective method for incorporating an azide group at an initiating chain end of poly(alkoxycarbonylmethylene) (PACM) is presented. Polymerization of diazoacetate using π-allylPdCl(Py) (Py = pyridine) as an initiator in the presence of 2-bromoethanol as a chain transfer agent (CTA) afforded a Br-capped PACM, which was subjected to nucleophilic substitution with tetrabutylammonium azide (TBAAZ) to yield an N3-capped PACM. The efficient progress of the two-step transformation was confirmed by chain-end characterization with MALDI-TOF-MS analyses. The use of additional pyridine was found to promote the ligand exchange from Pd–Cl to Pd–OCH2CH2Br, thus enabling us to prepare well-defined N3-capped PACMs with Mn in the range of 3000–5000. The utility of the N3-capped PACMs was demonstrated by the preparation of a 4-armed C1-star polymer containing PACM arms via a click reaction of the chain-end azide with a tetra-alkyne-substituted compound.

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2-溴乙醇介导的重氮乙酸酯链转移聚合-叠氮化反应合成叠氮化包覆的聚烷氧羰基亚甲基

摘要提出了在聚烷氧羰基亚甲基（PACM）的起始链端加入叠氮化物基团的有效方法。以π-烯丙基pdcl (Py) （Py =吡啶）为引发剂，以2-溴乙醇为链转移剂（CTA）聚合重氮乙酸酯，得到溴包覆PACM，并与叠氮化四丁基铵（TBAAZ）亲核取代，得到氮包覆PACM。利用MALDI-TOF-MS分析证实了两步转化的高效进行。发现额外的吡啶的使用促进了配体从Pd-Cl到Pd-OCH2CH2Br的交换，从而使我们能够制备具有良好定义的Mn在3000-5000范围内的n3 -cap pacm。通过链端叠氮化物与四炔取代化合物的咔嗒反应，制备了含有PACM臂的4臂c1星聚合物，证明了n3包封PACM的实用性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

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