Synthesis of High Molecular Weight Polymethacrylates with Polyhedral Oligomeric Silsesquioxane Moieties by Atom Transfer Radical Polymerization

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• 作者：Adrian Franczyk ; Hongkun He ; Joanna Burdy艅ska ; Chin Ming Hui ; Krzysztof Matyjaszewski ; Bogdan Marciniec
• 刊名：ACS Macro Letters
• 出版年：2014
• 出版时间：August 19, 2014
• 年：2014
• 卷：3
• 期：8
• 页码：799-802
• 全文大小：287K
• ISSN：2161-1653

文摘

A new polyhedral oligomeric silsesquioxane (POSS) methacrylate monomer, 1-(3-(methacryloyloxy)propyl)dimethylsiloxy-3,5,7,9,11,13,15-hepta(isobutyl)pentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane ((i-Bu)₇POSS-OSiMe₂-MA, 1), with a flexible spacer between the cubic POSS cage and methacrylate group was synthesized to reduce steric strain and thus achieve polymethacrylates (poly(POSS-MA)s) with high molecular weight (MW). Atom transfer radical polymerization (ATRP) of 1 at high monomer concentration (1 M, corresponding to ca. 85 wt % of 1) led to polymers with the absolute number-average MW, determined by multiangle laser light scattering, M_n,_MALLS = 2鈥?50鈥?00 (and apparent MW, measured by gel permeation chromatography with linear poly(methyl methacrylate) (PMMA) standards, M_n,GPC = 550鈥?00). Optimization of the reaction conditions, including the ATRP catalyst, targeted degrees of polymerization, monomer concentrations, as well as a monomer feeding, resulting in the first well-defined high MW polymers with POSS moieties.