【作者】 徐艳莲；

【导师】 胡炳环；

【作者基本信息】 福建师范大学 ， 高分子化学与物理， 2009， 博士

【摘要】 本文利用水辅助自组装制备了漆酚甲醛缩聚物(PUF)、漆酚缩醛胺聚合物(PUFD)、漆酚钛螯合高聚物(PUT)和漆酚钛螯合高聚物/羟基化多壁碳纳米管复合材料(PUT/CNT)等四种不同极性的漆酚基聚合物的多孔薄膜。首先,从具有漆酚分子结构特征和生漆膜优良理化特性的PUF的蜂窝状多孔聚合物薄膜入手,研究聚合物在高湿度条件下的成膜特性。实验结果表明:用水辅助自组装,可以制备出蜂窝状结构的PUF多孔膜。在多孔膜形成过程,有更多极性基团-OH朝向模板水滴,从而导致孔周围的含氧量升高。当环境湿度、潮湿气体流速和聚合物溶液量增大时,所形成的蜂窝状孔的规则性提高且孔径变大;38.1～88.9mg/mL浓度的PUF二硫化碳溶液都可用于水辅助自组装制备蜂窝状多孔膜;该PUF多孔膜对水的接触角在96～119°,为疏水性膜;经10%盐酸和10%NaOH浸泡3h后仍保留原来多孔膜的形貌。其次,以仍保持着漆酚的基本骨架,但部分漆酚酚羟基被封闭的漆酚钛螯合高聚物(PUT)和漆酚钛螯合高聚物/羟基化多壁碳纳米管复合材料(PUT/CNT)为成膜材料,用水辅助自组装制备多孔膜,并用反相气相色谱测试PUT和PUT/CNT的表面自由能,研究聚合物表面自由能对膜形貌的影响。实验结果表明:(1)以PUT为成膜物质,可以制得PUT多孔膜,但没有得到规则的蜂窝状结构。(2)用水辅助自组装可成功制备规则的蜂窝状PUT/CNT多孔膜,孔周围的极性基团-OH数比孔壁上的高。多孔膜的孔径随着聚合物溶液浓度的提高,环境湿度的下降呈减小趋势;溶液量较小时(5.0μL)得到二维单层的多孔膜,而溶液量较大(10.0和20.0μL)时,得到三维多层的多孔膜。(3)PUT和PUT/CNT均为弱的Lewis碱,PUT的Lewis酸常数K_a为0.1853,碱常数K_b为0.9662。PUT/CNT的Lewis酸常数K_a为0.2062,碱常数K_b为0.6250。与PUT相比,PUT/CNT的色散自由能和由酸碱作用引起的吸附自由能都比PUT大,有利于蜂窝状多孔膜的形成。(4)PUT/CNT多孔膜对水的接触角在110～119°,为疏水性膜,并具有优良的耐强酸、碱性和耐热性。最后,不在聚合物溶液表面吹潮湿气体的静态高湿环境下,以具有漆酚羟基又具有氨基或亚氨基的漆酚缩醛胺聚合物(PUFD)为成膜材料,用水辅助自组装制备多孔膜。实验结果表明:静态高湿环境下,用水辅助自组装制备PUFD多孔膜时,数均分子量要大于4.8×10~3才能得到蜂窝结构多孔膜。水面展开法更有利于形成单层的多孔膜,而固体基板展开法得到的是多层的多孔膜。当PUFD聚合物浓度为6.0mg/mL,环境相对湿度为90%时,用水面展开法制得的单层多孔膜的孔径分布较均匀。更多还原

【Abstract】 In this paper, the microporous films of four urushiol-based polymers differing in polarity have been successfully fabricated by water-assisted self-assembly in the moisture atmosphere. Furthermore, several influencing factors on the formation of urushiol-based polymers microporous films and the different morphologies, such as the polymer surface free energy, the concentration of the polymer solution, the moist airflow speed, the relative humidity in the atmosphere, and the substrates, etc, were investigated.Firstly, urushiol-formaldehyde polymer (PUF) honeycomb structured films have been successfully fabricated by water-assisted self-assembly. The films were characterized by Scanning Electronic Microscopy (SEM), Atomic Force Microscope(AFM) and Energy Dispersive Spectrometer(EDS), etc. The experimental results showed that the polarity group (-OH) quantity of the surrounding pore was higher than the pore wall. With the increase of the humidity of the atmosphere, the speed of the moisture airflow, and the volume of the solution, the pore size of PUF increased. Different from other literatures which could obtain regular pores only in low concentrations, the regular pores of PUF films were formed when the concentrations ranged from 38.1 to 88.9 mg/mL. Furthermore, PUF microporous films were hydrophobic, and the PUF films retained the original morphology after being immerged in 10% hydrochloric acid or 10% NaOH for 3h.Secondly, urushiol-titanium chelate polymer (PUT) and urushiol titanium chelate polymer/multi-walled carbon nanotube composite material (PUT/CNT) microporous films have been fabricated by water-assisted self-assembly. The films were characterized by SEM, AFM, EDS and the Laser Scanning Confocal Microscope(LSCM), etc. Inverse gas chromatography (IGC) was used to test the surface properties of PUT and PUT/CNT. The experimental results indicated that the regular honeycomb PUT/CNT microporous films could be successfully prepared by water-assisted self-assembly method, but PUT could (?)ot. Meanwhile, decreased humidity and increased solution concentration leaded to reducing pore size. Moreover, PUT/CNT’s surface free energy of the dispersive component and Lewis acid-base interactions were larger than that of PUT’s. The Lewis acidic number K_a of PUT and PUT/CNT was 0.1853 and 0.2062, while the basic number K_b of PUT and PUT/CNT was 0.9662 and 0.6250, respectively. The PUT/CNT porous films retained the original morphology after being immerged in 10% hydrochloric acid or 10% NaOH, xylene for 24h. The PUT/CNT porous films exhibited good thermal resistance.Lastly, in the static moisture atmosphere, urushiol-formaldehyde diethylenetriamine polymer (PUFD) microporous films have been successfully fabricated by water-assisted self-assembly. The comparison of the two methods indicated PUFD microporous films with monolayer could be fabricated by spreading on water but with multilayer by spreading on solid. Furthermore, several influencing factors on the formation of the PUFD microporous films and the different morphologies, such as the molecular weight, the concentration of the polymer solution, the relative humidity in the atmosphere and the substrates, were investigated. The results showed that the water surface, as a spreading substrate, was suitable to form orderly porous films for such a polymer. To get regular structure PUFD porous film, the number average molecular weight of PUFD should exceed 4.8×10~3. The monolayer film with a relative uniform pore size distribution could be formed from the polymer with concentration of 6.0 mg/mL at the relative humidity of 90% and room temperature by using a water surface.更多还原