【摘要】：Honeycomb膜是一種具有蜂窩狀結(jié)構(gòu)的微米尺寸均孔膜,以高濕度環(huán)境中沉積到揮發(fā)性聚合物溶液表面并規(guī)整排列的水滴作為模板制備得到。盡管成孔過程簡單,但傳統(tǒng)制備honeycomb膜的聚合物合成過程繁瑣,所得到的honeycomb膜也存在耐溶劑性、耐熱性差等問題,限制了其在苛刻環(huán)境中的應(yīng)用。將多孔膜交聯(lián)可以有效解決這一缺陷,光化學(xué)交聯(lián)具有高效、易操作、污染小等優(yōu)勢近年來逐漸得到研究者關(guān)注。本文首次以甲基丙烯酸縮水甘油酯的均聚物(PGMA),利用靜態(tài)呼吸圖案法,制備出高度規(guī)整的honeycomb膜,并通過陽離子光固化對多孔膜實現(xiàn)了交聯(lián)。1.通過熱自由基溶液聚合制備了不同分子量的線性PGMA,利用靜態(tài)呼吸圖案法,通過調(diào)控成孔過程中多種實驗參數(shù),制備出高度規(guī)整的honeycomb膜,利用SEM和激光直射實驗手段對所得多孔膜形貌及性質(zhì)進(jìn)行表征。結(jié)果表明,溶劑的種類對能否成孔起關(guān)鍵作用,在本實驗中,以CH2Cl_2和CHCl_3按照70:30 (體積比)互混作溶劑可以制備規(guī)整多孔膜;分子量為15K,45K,100K左右的聚合物,在合適的溶液濃度范圍內(nèi)能有效穩(wěn)定水滴而得到規(guī)整孔結(jié)構(gòu);在一定范圍內(nèi),孔徑隨環(huán)境濕度增加而線性增長。2.上述制備的honeycomb膜表面帶有大量可交聯(lián)的環(huán)氧基團(tuán),通過陽離子引發(fā)劑溶液浸泡光照對多孔膜實現(xiàn)快速交聯(lián)。通過SEM、AFM等對交聯(lián)后多孔膜進(jìn)行表征。結(jié)果表明,與未交聯(lián)膜相比,交聯(lián)后孔的結(jié)構(gòu)保存完好,可以耐受CH2Cl2, CHCl3, THF,丙酮等有機(jī)溶劑長達(dá)一周,其耐熱性提高了 125℃。3.交聯(lián)后的多孔膜提供二氧化硅在表面生長的化學(xué)位點(diǎn),將其作為模板,通過化學(xué)氣相沉積法,得到孔徑和壁厚可調(diào)的可獨(dú)立支撐的無機(jī)二氧化硅的honeycomb膜,在光電領(lǐng)域有潛在應(yīng)用。同時,分別以剝離前后的聚合物多孔膜作為模板,選擇性制備了二氧化硅的微米碗和微米盤,在細(xì)胞培養(yǎng)及載體領(lǐng)域有潛在的應(yīng)用價值。
[Abstract]:Honeycomb film is a kind of micron uniform pore film with honeycomb structure. The water droplets deposited on the surface of volatile polymer solution in high humidity environment and arranged regularly are prepared as templates. Although the pore forming process is simple, the traditional polymer synthesis process of honeycomb film is tedious. The obtained honeycomb film also has some problems, such as solvent resistance, poor heat resistance and so on, which limits its application in harsh environment. This defect can be effectively solved by cross-linking porous membranes. Photochemical crosslinks have been paid more and more attention by researchers in recent years because of their advantages of high efficiency, easy operation and low pollution. In this paper, the highly structured honeycomb film was prepared by static respiratory pattern method with glycidyl methacrylate homopolymer (PGMA), for the first time, and the porous film was crosslinked by cationic light curing. Linear PGMA, with different molecular weight was prepared by thermal free radical solution polymerization by static respiratory pattern method, and highly regular honeycomb films were prepared by adjusting various experimental parameters in the process of pore formation. The morphology and properties of the porous films were characterized by SEM and laser direct emission experiments. The results show that the type of solvent plays a key role in the formation of pores. In this experiment, regular porous membranes can be prepared by mixing CH2Cl_2 and CHCl_3 with 70:30 (volume ratio); the polymer with molecular weight of 15K, 45K and 100K can effectively stabilize the water droplets in a suitable solution concentration range to obtain the regular pore structure; in a certain range, the pore size increases linearly with the increase of environmental humidity. The surface of the prepared honeycomb film has a large number of crosslinked epoxy groups, and the porous film can be crosslinked rapidly by soaking in cationic initiator solution. The crosslinked porous membranes were characterized by SEM,AFM et al. The results showed that compared with the uncrosslinked membrane, the structure of the crosslinked pores was well preserved, and it could withstand CH2Cl2, CHCl3, THF, acetone and other organic solvents for as long as one week, and its heat resistance was increased by 125 鈩，

本文編號：2508001