Grafting of organic polymer in pores of macroporous silica vesicle material

doi:10.11949/j.issn.0438-1157.20160415

Abstract

Abstract:

Macroporous vesicle material with more than 100 nm diameter was synthesized via hydrothermal method using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as template and tetramethyl orthosilicate (TMOS) as silica source. Moreover, the radical initiators with silane coupling groups such as (2-bromo-2-methylpropionyl)oxy-butyl triethoxysilane (BPE) and (2-bromo-2-methylpropionyl) oxy-butyl chlorodimethylsilane (BPCM) were synthesized by a two-step method. Then BPE and BPCM were grafted onto the inner surface of vesicle via coupling reaction of silane group and Si-OH. The elemental analysis confirmed that BPCM gave higher grafting efficiency. After that the atom transfer radical polymerizations (ATRP) of methyl methacrylate (MMA) and butyl methacrylate (BMA) were initiated in the pores of vesicle, respectively, and the monomers gradually reacted on surface-initiators to form polymer brushes. Transmission electron microscopy (TEM) results suggested that the vesicles retained after grafting of polymers into the inner surface of material successfully. The grafted polymers were cleaved by chemical process and analyzed by gel permeation chromatography (GPC). The number average molecular weights (M_n) of PMMA and PBMA were 7600 and 11400, respectively, the polydispersity indexes (PDI) of PMMA and PBMA were both 1.25.

Key words: vesicle material, pore, in-situ grafting, radical, polymerization, composites

摘要：

以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物（P123）为模板剂、正硅酸甲酯（TMOS）为硅源，采用水热法合成出孔径大于100 nm的硅基囊泡材料。同时采用两步法合成出带有硅烷偶联基团的有机自由基引发剂2-溴-2-甲基丙酸丁酯基三乙氧基硅烷（BPE）和2-溴-2甲基丙酸丁酯基二甲基氯硅烷（BPCM）。再利用偶联基团与囊泡材料孔道内表面的硅羟基偶联反应将自由基引发剂BPE和BPCM分别接枝到囊泡内表面，元素分析发现BPCM具有更高的接枝效率。然后在囊泡孔道内分别引发烯烃单体甲基丙烯酸甲酯（MMA）和甲基丙烯酸丁酯（BMA）的原子转移自由基聚合（ATRP）反应，使单体在表面自由基上逐一反应形成聚合物刷。透射电镜（TEM）表征结果表明，孔道内表面接枝上了聚合物后囊泡保持较为完好。通过化学方法将聚合物切割下来，凝胶渗透色谱（GPC）分析发现接枝的PMMA和PBMA的数均分子量（M_n）分别为7600和11400，分子量分布指数（PDI）均为1.25。

关键词: 囊泡材料, 孔道, 原位接枝, 自由基, 聚合, 复合材料

CLC Number:

TQ028.8

REN Shenyong, ZHANG Ka, YAN Hui, ZHANG Jianhua, ZENG Penghui, GUO Qiaoxia, SHEN Baojian. Grafting of organic polymer in pores of macroporous silica vesicle material[J]. CIESC Journal, 2016, 67(8): 3507-3514.

任申勇, 张卡, 闫慧, 张建华, 曾鹏晖, 郭巧霞, 申宝剑. 在大孔硅基囊泡材料孔道内原位接枝有机聚合物[J]. 化工学报, 2016, 67(8): 3507-3514.

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