本文選題：紫外輻照 + 羥基丙烯酸酯�。� 參考：《天津工業(yè)大學(xué)》2016年博士論文

【摘要】：聚砜(PSF)、聚丙烯(PP)等是常見的有機聚合物膜材料,但由于它們具有較強的疏水性,在應(yīng)用過程中極易被污染,造成膜通量的衰減、膜利用率和膜壽命的降低以及膜應(yīng)用成本的增高,因此開發(fā)新型親水性膜或?qū)ΜF(xiàn)有膜材料進行親水改性具有重要理論意義和實用價值。紫外輻照法具有反應(yīng)條件溫和、工藝簡單、波長連續(xù)可調(diào)節(jié)且反應(yīng)只能在材料表面發(fā)生等優(yōu)點,是一種常用的表面改性方法。為解決常見的有機聚合物膜易污染的問題,本文采用紫外光輻照接枝法,分別通過添加光敏劑與否、改變單體的相對分子質(zhì)量大小及調(diào)整單體的親水性官能團的數(shù)目和分布對中空纖維膜的表面結(jié)構(gòu)進行調(diào)控,并對其性能進行表征。優(yōu)化中空纖維膜表面改性方法,制備出親水性和抗污染性良好的中空纖維膜。本文的具體研究內(nèi)容和結(jié)論如下：首先,采用間歇式紫外輻照法,以聚砜和聚丙烯中空纖維膜為探針,以丙烯酸(AA)和丙烯酸羥乙酯(HEA)為單體,研究光敏劑存在與否對膜表面結(jié)構(gòu)及性能的影響。結(jié)果表明,光敏劑存在與否對膜表面結(jié)構(gòu)有較大影響。無光敏劑時,經(jīng)紫外輻照后聚砜中空纖維膜表面雖有親水性單體成功接枝,但聚砜膜基體結(jié)構(gòu)受到損傷,表面孔結(jié)構(gòu)增大,改性膜的截留率降低,而聚丙烯膜表面基本沒有發(fā)現(xiàn)單體的接枝；存在光敏劑時,紫外輻照后,聚砜和聚丙烯中空纖維膜表面均有單體成功接枝,膜表面結(jié)構(gòu)得到調(diào)控,改善了膜的親水性和抗污染性。其次,采用間歇式紫外輻照法,以PSF中空纖維膜為探針,以自制的丙烯酸羥乙酯(HEA)、丙烯酸羥丙酯(3HPA)、丙烯酸丁二醇單酯(4HBA)和丙烯酸三羥甲基丙烷單酯(TMPAA)四種不同的羥基丙烯酸酯為單體,研究了單體的相對分子質(zhì)量大小對膜表面結(jié)構(gòu)及性能的影響。結(jié)果表明,經(jīng)過紫外輻照后,幾種單體均能夠在膜表面成功接枝,均能在膜表面上引入親水性的羥基官能團,使膜表面結(jié)構(gòu)發(fā)生改變,并使膜的親水性和抗污染性得到提高。相同條件下,羥基丙烯酸酯的相對分子質(zhì)量越大,分子的碳鏈越長,其在膜表面的接枝密度越低,引入膜表面的羥基密度越小,其對膜親水性及抗污染性的提高程度也越小；但適當(dāng)?shù)卦黾庸δ軉误w中親水性官能團羥基的數(shù)目可以增大膜表面的羥基含量,進而可以有效地改善膜表面的親水性和抗污染性。當(dāng)TMPAA在PSF膜上的接枝密度為3.02 mmol.m-2時,膜的外表面接觸角由原膜的80°降低到改性膜的46°,純水通量由原膜的115 L.m-2.h-1增加到改性膜的173 L.m-2.h-1,對BSA的截留率由88.6%增加到93.4%,過濾BSA溶液的通量衰減率由66.4%降低到26.9%,清洗后PSF-g-TMPAA膜的通量恢復(fù)率也由68.6%增加到90.5%。此外,為進一步實現(xiàn)工業(yè)化,提高實際應(yīng)用價值,采用連續(xù)化紫外輻照法,以PP中空纖維膜為探針,以自制的丙烯酸羥乙酯(HEA)、丙烯酸甘油單酯(GA)和丙烯酸季戊四醇單酯(PEA)三種不同的羥基丙烯酸酯為單體,研究了羥基的數(shù)目和分布對膜表面結(jié)構(gòu)及性能的影響。研究發(fā)現(xiàn),使用不同單體時,可以得到不同羥基數(shù)目和分布的聚丙烯中空纖維改性膜,有效改善膜表面的化學(xué)結(jié)構(gòu)和形貌。另外,通過使用不同單體對改性膜表面進行結(jié)構(gòu)設(shè)計,可以顯著增加膜表面的親水性和抗污染性。相同條件下,膜表面的親水性和抗污染性隨著引入膜表面的羥基數(shù)目的增加而增強；而羥基分布的影響相對復(fù)雜,接枝密度較低時,羥基分布越集中,膜表面的親水性和抗污染性越好,接枝密度較高時,羥基分布對膜性能的影響不明顯。當(dāng)PEA在PP中空纖維膜上的接枝密度為0.838 mmol.m-2時,膜表面的親水性和抗污染性得到顯著改善,改性膜表面的水滴僅需6.3 s就完全消失,PP-g-PEA膜的純水通量大約增加到原膜純水通量的4.5倍,膜的通量衰減由原膜的56%下降為改性膜的21%,清洗后的膜的通量恢復(fù)率由原膜的34%增加到改性膜的85%。本文的研究表明,通過添加光敏劑條件下親水性功能單體在膜表面的紫外輻照接枝聚合,可以實現(xiàn)膜表面結(jié)構(gòu)的調(diào)控,在膜表面引入親水性官能團的同時不損傷膜基體結(jié)構(gòu),能夠有效提高膜表面的親水性和抗污染性。另外,可以通過改變功能單體的相對分子質(zhì)量大小以及親水性官能團數(shù)目和分布對膜表面結(jié)構(gòu)進行有效調(diào)控,本文的研究為親水性膜的表面結(jié)構(gòu)設(shè)計提供了一定的理論基礎(chǔ),對新型親水膜的制備具有指導(dǎo)意義。
[Abstract]:Polysulfone (PSF), polypropylene (PP) is a common organic polymer film materials, but because they have strong hydrophobicity, can easily be contaminated in the application process, causes attenuation of membrane flux increased, and reduce the rate of membrane life and membrane application cost by membrane, so the development of a new type of hydrophilic membrane or it has important theoretical significance and practical value of hydrophilic modification of existing membrane materials. Ultraviolet irradiation method has mild reaction condition, simple process, can be adjusted and the advantages of wavelength continuous reaction only on the surface of the material occurs, is a commonly used method of surface modification of organic polymer film. In order to solve the common problems of pollution. This paper adopts UV irradiation grafting method, respectively, by adding photosensitizer or not, change the number of molecular weight and adjusting the monomer hydrophilic functional groups and the distribution of surface structures of hollow fiber membrane. For regulation, and its properties were characterized. The optimization of membrane surface modification method, preparation of hollow fiber membrane hydrophilicity and anti pollution well. The specific contents and conclusions are as follows: first, the use of intermittent UV irradiation method, using polysulfone and polypropylene hollow fiber membrane as a probe to acrylic acid (AA) and 2-hydroxyethyl acrylate (HEA) as the monomer, the existence of photosensitizer on the structure and properties of the film surface is investigated. The results show that the existence of photosensitizer on the membrane surface structure has great influence. Without photosensitizer, after ultraviolet irradiation of polysulfone hollow fiber membrane surface is hydrophilic monomer the successful grafting, but the polysulfone membrane matrix structure damage, increase the surface pore structure, the modified membrane interception rate decreased, and the polypropylene membrane has uncovered graft monomer; existence of photosensitizer, ultraviolet irradiation, and poly sulfone hollow polypropylene Fiber membrane surface of both monomers were grafted, membrane surface structure control, improve the membrane hydrophilicity and anti fouling properties. Secondly, using intermittent UV irradiation, the PSF hollow fiber membrane as a probe to hea - (HEA), hydroxypropyl acrylate (3HPA), butyl glycol monoester (4HBA) and acrylic acid three trimethylolpropane ester (TMPAA) four different hydroxyl acrylate as monomer, studied the effect of molecular weight of monomer on the structure and properties of the membrane surface. The results showed that after UV irradiation, several monomers were successfully grafted on the surface of the film can be that can introduce hydrophilic hydroxyl groups on the membrane surface, the membrane structure changed, and the membrane hydrophilicity and antifouling properties were improved. Under the same conditions, the relative molecular mass of hydroxyl acrylate larger molecules with longer carbon chain on the membrane surface, the The grafting density is low, the membrane surface hydroxyl density is small, the membrane hydrophilicity and anti fouling properties improved degree is smaller; but due to increasing the number of hydroxyl content of hydroxyl functional monomer in hydrophilic functional groups can increase the membrane surface, which can effectively improve the surface hydrophilicity and anti pollution. When the grafting density of TMPAA on PSF film is 3.02 mmol.m-2, the outer membrane surface contact angle from the original film 80 degrees down to 46 degrees of the modified membrane, pure water flux increased from 115 L.m-2.h-1 to the original film modified film 173 L.m-2.h-1, the retention of BSA increased by 88.6% 93.4%, the filtration of BSA solution flux decay rate decreased from 66.4% to 26.9%, after cleaning the PSF-g-TMPAA membrane flux recovery rate also increased from 68.6% to 90.5%., in addition, to further realize the industrialization, improve the practical application value, with the continuous ultraviolet irradiation method, PP hollow fiber Fiber membrane probe with ethyl acrylate (HEA), a self-made acrylic acid monoglyceride (GA) and acrylic acid pentaerythritol monoester (PEA) three different hydroxyl acrylate monomers on the hydroxyl number and distribution effects on the structure and properties of the membrane surface. The study found that the use of different monomers that can get the number and distribution of polypropylene hollow fiber membrane modified by hydroxyl groups, the chemical structure and morphology can effectively improve the membrane surface. In addition, the paper designs the structure of the modified membrane surface using different monomers, can significantly increase the membrane surface hydrophilicity and anti fouling properties. Under the same condition, the surface hydrophilic membrane and pollution resistance increases with the introduction of surface hydroxyl substituents increased; and the effect of hydroxyl distribution is relatively complex, lower grafting density, hydroxyl distribution is concentrated, the membrane surface hydrophilicity and antifouling properties better, grafting density When high hydroxyl distribution effects on membrane properties is not obvious. When the grafting density of PEA in the PP hollow fiber membrane was 0.838 mmol.m-2, the membrane surface hydrophilicity and anti fouling resistance are significantly improved, the modified membrane surface water is only 6.3 s completely disappeared, pure water flux increased about PP-g-PEA film to 4.5 times the original water flux of membrane, the membrane flux attenuation decline for the modified film 21% by the original film 56%, after cleaning the membrane flux recovery rate increased from 34% to the original film of modified 85%. film in this paper showed that the hydrophilic functional monomer adding photosensitizer conditions in ultraviolet polymerization graft polymerization of the membrane surface, may regulate membrane surface structure, the introduction of hydrophilic functional groups on the membrane surface without damaging the substrate structure, can effectively improve the surface hydrophilicity and anti fouling properties. In addition, by changing the relative points of functional monomer The size and distribution of the hydrophilic functional groups can effectively control the surface structure of the membrane. This study provides a theoretical basis for the design of the surface structure of the hydrophilic membrane, and has a guiding significance for the preparation of the new hydrophilic membrane.

【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TQ051.893

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