Polydimethylsiloxane-(PDMS-) grafted fluorocopolymers by a "grafting through" strategy based on atom transfer radical (Co)polymerization
Polydimethylsiloxane-(PDMS-) grafted fluorocopolymers by a "grafting through" strategy based on atom transfer radical (Co)polymerization
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DOI：
10.1021/ma070845w
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发表时间：
2007-10-02
期刊：
影响因子：
5.5
通讯作者：
Wooley, Karen L.
中科院分区：
文献类型：
--
作者：
Cheng, Chong;Powell, Kenya T.;Wooley, Karen L.
基于原子转移自由基聚合（ATRP）技术，使用甲基丙烯酰氧基丙基封端的PDMS（PDMSMA）作为大分子单体，通过“接枝”方法合成了三种具有不同支化特征的PDMS接枝含氟共聚物。具有线性氟化主链和线性PDMS接枝物的共聚物1是通过2,3,4,5,6-五氟苯乙烯(PFS)与PDMSMA的共聚制备的。共聚物 2 具有超支化氟化主链和线性 PDMS 接枝物，是通过单体、对氯甲基苯乙烯 (CMS) 与 PFS 和 PDMSMA 进行自缩合乙烯基共聚 (SCVCP) 来制备的。具有超支化氟化核和线性 PDMS 接枝物的共聚物 3 是通过 PDMSMA 的 ATRP 制备的，由氯化苄官能化的超支化含氟共聚物（通过 PFS 和 CMS 的 SCVCP 获得）引发。采用H-1、C-11和F-19核磁共振波谱、凝胶渗透色谱、元素分析、热重分析和溶解度测试等一系列表征方法来研究反应动力学以及这些共聚物的组成、分子量和性能。
Three types of PDMS-grafted fluorocopolymers with various branching features were synthesized based on atom transfer radical polymerization (ATRP) techniques via a "grafting through" approach using methacryloxypropyl-terminated PDMS (PDMSMA) as macromonomer. Copolymers 1, with a linear fluorinated backbone and linear PDMS grafts, were prepared by copolymerizations of 2,3,4,5,6-pentafluorostyrene (PFS) with PDMSMA. Copolymers 2, with a hyperbranched fluorinated backbone and linear PDMS-based grafts, were prepared by self-condensing vinyl copolymerization (SCVCP) of an inimer, p-chloromethylstyrene (CMS), with PFS and PDMSMA. Copolymers 3, with a hyperbranched fluorinated core and linear PDMS grafts, were prepared by ATRP of PDMSMA, initiated by benzylic chloride-functionalized hyperbranched fluorocopolymer (obtained by SCVCP of PFS and CMS). A series of characterization methods, including H-1, C-11, and F-19 NMR spectroscopies, gel permeation chromatography, elemental analysis, thermogravimetric analysis, and solubility tests, were used to investigate the reaction kinetics, and the compositions, molecular weights, and properties of these copolymers.