Subnanoporous Highly Oxygen Permselective Membranes from Poly(conjugated hyperbranched macromonomer)s Synthesized by One-Pot Simultaneous Two-Mode Homopolymerization of 1,3-Bis(silyl)phenylacetylene Using a Single Rh Catalytic System: Control of Their Structures and Permselectivities,Macromolecules

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Subnanoporous Highly Oxygen Permselective Membranes from Poly(conjugated hyperbranched macromonomer)s Synthesized by One-Pot Simultaneous Two-Mode Homopolymerization of 1,3-Bis(silyl)phenylacetylene Using a Single Rh Catalytic System: Control of Their Structures and Permselectivities
Macromolecules ( IF 5.1 ) Pub Date : 2017-09-13 00:00:00 , DOI: 10.1021/acs.macromol.7b01458
Jianjun Wang , Jun Li , Toshiki Aoki ₁ , Takashi Kaneko ₁ , Masahiro Teraguchi ₁ , Zhichun Shi , Hongge Jia

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Novel well-defined complex polymers, polymers of acetylene-type macromonomers having silylene–vinylene–phenylene–ethynylene hyperbranches, investigated as a new class of subnanoporous oxygen permselective membrane materials, were synthesized very easily by one-pot simultaneous two-mode homopolymerization of a single monomer with a single catalyst. For this “simultaneous polymerization” we synthesized AB₂-type monomers (1,3-bis(dimethylsilyl)phenylacetylenes) containing one terminal triple bond and two Si–H groups. The resulting poly(hyperbranched macromonomer)s had high molecular weights, low densities, high solubility, and good self-membrane forming ability. They had higher oxygen permselectivities (α = P_O₂/P_N₂) than any other reported polymers having similar oxygen permeabilities (P_O₂). These excellent polymer membranes could be obtained only by the simultaneous polymerization. In the one-pot simultaneous polymerization, the two different modes of polymerizations, i.e., addition polymerization of the triple bond and polyaddition of the triple bond and two SiH groups in the single monomer, occurred simultaneously by using one catalytic system, i.e., [Rh(norbornadiene)Cl]₂/various amines. The ratio of the branches (RB), i.e., the addition polymerization and the polyaddition, could be controlled by changing the amine cocatalysts. Their oxygen permselectivities could be adjusted by controlling the polymer structures including RB.

中文翻译：

单锅同时Rh催化体系由1,3-双（甲硅烷基）苯基乙炔的一锅同时双模均聚反应合成的聚（共轭超支化大分子单体）亚纳孔高氧选择性通透膜：控制其结构和通透性

新型定义明确的复杂聚合物，即具有亚甲硅基-亚乙烯基-亚苯基-亚乙炔基高支链的乙炔型大分子单体的聚合物，被研究为一类新型的亚纳孔氧渗透选择性膜材料，可通过一锅同时双模均聚反应很容易地合成。单一单体和单一催化剂。对于这种“同时聚合”，我们合成了含有一个末端三键和两个Si-H基团的AB ₂型单体（1,3-双（二甲基甲硅烷基）苯基乙炔）。所得的聚（超支化大分子单体）具有高分子量，低密度，高溶解度和良好的自膜形成能力。它们具有更高的氧选择性（α= P _{O ₂} / P _{N ₂}）比任何其他报告的具有相似的氧渗透性（P _{O ₂}）的聚合物都要好。这些优异的聚合物膜只能通过同时聚合来获得。在一锅同时聚合中，通过使用一种催化体系，即[Rh]，同时发生两种不同的聚合方式，即三键的加成聚合和单单体中的三键与两个SiH基团的加成聚合。（降冰片二烯）Cl] ₂ /各种胺。支链（RB）的比例，即加成聚合和加聚，可以通过改变胺助催化剂来控制。可以通过控制包括RB在内的聚合物结构来调节其氧渗透性。

更新日期：2017-09-13

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