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材料研究学报  2014, Vol. 28 Issue (1): 8-14    DOI: 10.11901/1005.3093.2013.678
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蝌蚪型POSS丙烯酸酯嵌段共聚物及其蜂窝状多孔膜的制备和性能
余韬,马晓燕(),李毅卓,栗志广,强秀
西北工业大学空间应用物理与化学教育部重点实验室和陕西省高分子科学与技术重点实验室 西安 710129
Synthesis of Tadpole POSS Acrylate Block Copolymer as well as Preparation and Performance of Honeycomb-patterned Films from the Block Copolymer
Tao YU,Xiaoyan MA(),Yizhuo LI,Zhiguang LI,Xiu QIANG
The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education and the Key Laboratory of Polymer Science and Technology, Shaanxi Province, School of Science, Northwestern Polytechnical University,Xi’an, 710129
引用本文:

余韬,马晓燕,李毅卓,栗志广,强秀. 蝌蚪型POSS丙烯酸酯嵌段共聚物及其蜂窝状多孔膜的制备和性能[J]. 材料研究学报, 2014, 28(1): 8-14.
Tao YU, Xiaoyan MA, Yizhuo LI, Zhiguang LI, Xiu QIANG. Synthesis of Tadpole POSS Acrylate Block Copolymer as well as Preparation and Performance of Honeycomb-patterned Films from the Block Copolymer[J]. Chinese Journal of Materials Research, 2014, 28(1): 8-14.

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摘要: 

采用一锅逐步加料的原子转移自由基聚合方法(ATRP)制备了一种蝌蚪型多面体低聚倍半硅氧烷(POSS)丙烯酸酯嵌段共聚物, 并用静态呼吸图法制备该共聚物蜂窝状结构的多孔膜, 研究成膜条件如溶剂种类、聚合物浓度、相对湿度等对聚合物多孔膜形貌的影响, 以及空气/硅片、空气/水和空气/冰3种成膜界面对膜形貌的影响。结果表明, 在空气/硅片界面上, 以三氯甲烷为溶剂, 环境相对湿度为80%, 浓度为20 mg·mL-1时, 可形成圆形孔的多孔膜, 孔排列成六方形; 在相同的条件下在空气/水和空气/冰界面上均可制备出类似规整形貌的多孔结构, 但多孔膜的孔径、孔间距有很大的不同, 在空气/冰界面上的孔径更小、孔间距更窄。这种多孔膜具有良好的疏水性, 且其接触角随着孔径的减小而增大; 该多孔膜还具有良好的耐强酸强碱性和耐热性能。

关键词 有机高分子材料多孔膜呼吸图法嵌段共聚物界面疏水性能耐热性能    
Abstract

A honeycomblike porous film has been fabricated from a homogeneous solution of tadpole POSS acrylate block copolymer (POSS-PMMA-b-PS), which was made via atom transfer radial polymerization (ATRP) polymerization in one pot, using the static breath figures method. Taking into account of the formation mechanism of the pore, the influencing factors, such as the kind of solvent, the concentration of the solution and relative humidity for the formation of self-assembled block copolymer membrane, have been evaluated, and especially, the effects of interfaces, including air/glass wafer, air/water and air/ice interfaces, were investigated. The results show that cycloidal bubble arrays can be prepared when chloroform was chosen as solvent, concentration of POSS-PMMA-b-PS was 20 mgmL-1, relative humidity was 80%, and the solution was cast on the air/glass wafer interface; well-patterned membrane can also be prepared when the solution was cast on air/water and air/ice interfaces in the same condition; nevertheless, the pore size and hole spacing of the latter was much smaller. The result of static contact angle with water analysis shows that this porous film has good hydrophobic performance, and the contact angle increases with the decrease of pore size; the porous film shows excellent resistance to acid, alkaline and heat.

Key wordsorganic polymer materials    porous membranes    breath figures    block copolymer    interfaces    hydrophobicity    heat resistance
收稿日期: 2013-09-17     
图1  蝌蚪型嵌段共聚物的1H NMR谱和GPC曲线
图2  分别用三氯甲烷、二氯甲烷和四氢呋喃为溶剂使用20 mg· mL?1嵌段物溶液在空气/硅片界面上制备的多孔膜形态
图3  聚合物浓度提高对80% RH时在空气/硅片界面上多孔膜形貌的影响
图4  20 mg·mL?1聚合物三氯甲烷溶液在空气/硅片界面成膜,相对湿度提高对膜形态的影响
RH Pore size/μm Hole spacing/μm
60% 2.05±0.19 0.39±0.14
70% 2.17±0.16 0.43±0.14
75% 2.35±0.20 0.30±0.08
80% 2.46±0.20 0.92±0.15
90% -- --
表1  多孔膜在不同相对湿度下孔的分布
图5  20 mg·mL?1聚合物三氯甲烷溶液在空气/硅片、空气/水和空气/冰界面形成的多孔膜形态
Interface Pore size/μm Hole spacing/μm
air/glass wafer 2.46±0.20 0.92±0.15
air/water 1.39±0.20 0.32±0.20
air/ice 0.85±0.21 0.54±0.15
表2  不同界面上多孔膜孔的分布
图6  平面膜(相对湿度15%)和不同孔径多孔膜的静态接触角
图7  聚合物多孔膜在处理前及在3 mol·L?1盐酸溶液和氢氧化钠溶液中浸泡24 h 后的形态
图8  多孔膜在不同温度的热空气中热老化1 h后的形态
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