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AB单体的熊田-玉尾催化剂转移缩聚聚合反应：合成结构明确的超支化聚（噻吩撑-亚苯基）

Kumada-Tamao Catalyst-Transfer Condensation Polymerization of AB Monomer: Synthesis of Well-Defined Hyperbranched Poly(thienylene-phenylene).

作者信息

Ohta Yoshihiro, Hirota Toshiki, Yamamoto Arisa, Yokozawa Tsutomu

机构信息

Department of Materials and Life Chemistry, Faculty of Engineering, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama, 221-8686, Japan.

Department of Applied Chemistry, Faculty of Chemistry and Biochemistry, Kanagawa University, Rokkakubashi, Kanagawaku, Yokohama, 221-8686, Japan.

出版信息

Macromol Rapid Commun. 2025 May;46(9):e2401153. doi: 10.1002/marc.202401153. Epub 2025 Feb 2.

DOI:10.1002/marc.202401153
PMID:39895202
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12051736/
Abstract

The synthesis of well-defined hyperbranched aromatic polymer by Kumada-Tamao catalyst-transfer condensation polymerization of AB monomer is investigated. Grignard monomer 2 is generated by treatment of 2-(3,5-dibromophenyl)-3-hexyl-5-iodothiophene (1) with 1.0 equivalent of isopropylmagnesium chloride in THF at 0 °C for 1 h and subsequently polymerized with Ni(dppe)Cl at room temperature for 1 h. The molecular weight of the obtained polymer increases linearly up to ≈30 000 in proportion to the ratio of [consumed 2] /[Ni(dppe)Cl] and in proportion to the conversion of 2, while a narrow molecular weight distribution is maintained (M/M ≤ 1.12). The matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum shows almost a single series of peaks due to polymer with hydrogen at one end and bromine at the other, as in the case of Kumada-Tamao catalyst transfer condensation polymerization of AB monomers. The degree of branching (DB) of the obtained polymers is 0.70-0.75, irrespective of the degree of polymerization. These results indicate that the polymerization of 2 proceeds in a chain-growth polymerization manner through the intramolecular catalyst transfer mechanism, affording hyperbranched polymer with higher DB than the theoretical DB value of 0.5 in conventional polycondensation of AB monomers.

摘要

研究了通过AB单体的熊田-玉尾催化剂转移缩聚反应合成结构明确的超支化芳香族聚合物。格氏单体2是通过在0℃下于四氢呋喃中用1.0当量的异丙基氯化镁处理2-(3,5-二溴苯基)-3-己基-5-碘噻吩(1)1小时，随后在室温下与Ni(dppe)Cl聚合1小时而生成的。所得聚合物的分子量与[消耗的2]/[Ni(dppe)Cl]的比例以及2的转化率成比例地线性增加至约30000，同时保持窄的分子量分布(M/M≤1.12)。基质辅助激光解吸/电离飞行时间(MALDI-TOF)质谱显示，与AB单体的熊田-玉尾催化剂转移缩聚反应情况一样，几乎是一系列单一的峰，这是由于聚合物一端为氢，另一端为溴。所得聚合物的支化度(DB)为0.70-0.75，与聚合度无关。这些结果表明，2的聚合反应通过分子内催化剂转移机制以链增长聚合方式进行，得到的超支化聚合物的DB高于AB单体常规缩聚反应中理论DB值0.5。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/ec191e6aef5a/MARC-46-2401153-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/cbae3bea111a/MARC-46-2401153-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/ad0ff36b5b6d/MARC-46-2401153-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/38047984b8e5/MARC-46-2401153-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/7c4f340e7ae9/MARC-46-2401153-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/f390c92bb174/MARC-46-2401153-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/a30650004e7d/MARC-46-2401153-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/0196390709a6/MARC-46-2401153-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/ec191e6aef5a/MARC-46-2401153-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/cbae3bea111a/MARC-46-2401153-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/ad0ff36b5b6d/MARC-46-2401153-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/38047984b8e5/MARC-46-2401153-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/7c4f340e7ae9/MARC-46-2401153-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/f390c92bb174/MARC-46-2401153-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/a30650004e7d/MARC-46-2401153-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/0196390709a6/MARC-46-2401153-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f9af/12051736/ec191e6aef5a/MARC-46-2401153-g006.jpg

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