基于聚磺酸甜菜碱和聚乙二醇的抗污染表面构建及其性能研究

发布时间：2018-06-22 15:49

  本文选题：抗污染表面 + 聚磺酸甜菜碱　； 参考：《浙江大学》2015年博士论文

【摘要】：表面污染在生物医用材料、海洋作业和膜分离技术领域中是普遍存在的沉珂顽疾。解决的常用方法就是构建抗污染表面。目前,聚乙二醇(PEG)和以聚磺酸甜菜碱(PSBMA)为例的两性离子聚合物是最为常用的两种用于亲水化改性的抗污染材料。本论文旨在利用PSBMA和PEG超高的亲水性,探究简便有效的抗污染表面构建方法,并比较两种聚合物改性涂层的抗污染性和稳定性。具体研究工作主要围绕以下几个方面展开：采用钢丝网作为模型表面,选用PSBMA作为抗污染材料与多巴胺混合,通过多巴胺在碱性溶液中的氧化自聚和优异的粘附力将PSBMA'修饰在表面。借助XPS和FESEM等分析手段表征改性前后钢丝网的形貌与组成变化。PSBMA/PDA改性钢丝网具有水下超疏油与抗油滴粘附特性,其水下油接触角可以提高至158.6±8.0°,而滚动角只有3.9°。同时,涂层在有机溶剂和海水长时间浸泡下依然保持稳定。采用相同方法为聚丙烯微孔膜(PPMM)构建了PSBMA/PDA改性表面。改性膜在水接触角和通量测试中表现出极强的亲水化,也赋予膜表面优异的抗蛋白质吸附性能。但是PEG并不适用于相同的共沉积方法。随着PEG浓度的提高,表面沉积密度会大幅度下降,所构建的表面对牛血清白蛋白(BSA)具有极强的吸附,说明通过PEG/PDA共沉积构建的改性涂层并不具有抗污染性能。以天然多酚单宁酸(TA)作为组装单元,用以研究比较上述聚合物的LBL组装过程。借助紫光吸收光谱和QCM来监测组装过程,采用FT-IR/MR、XPS、VASE以及AFM对组装层的化学组成与形貌进行表征。结果表明PSBMA和TA之间会形成静电相互作用,使得表面可以在pH 4-10之间的溶液以及盐溶液中保持稳定。相比之下,PEG和TA的组装驱动力是弱的氢键相互作用,其增长符合指数型增长曲线,但涂层在碱性溶液下就分解洗脱。同时,(PSBMA/TA)n;表面具有良好的抗蛋白质吸附效果,可以将三种模型蛋白BSA、溶菌酶(Lys)和血红蛋白(Hgb)的吸附量降低至328,357, and 509 ng/cm2。采用紫外光辐照接枝聚合方法实现了SBMA和甲基丙烯酸聚乙二醇酯(OEGMA)在PPMM表面的接枝聚合,所获得的两种改性膜都具有高的亲水性和良好的抗蛋白质吸附性能。但它们在H2O2/Cu2+和NaCIO溶液中的氧化稳定性却大为不同。FT-IR/ATR、XPS和TOF-SIM结果表明PSBMA的降解速率要大于POEGMA,主要发生了酯键的水解和磺酸甜菜碱的离去。经过氧化降解,PSBMA接枝膜的水接触角从36°增加到110°,同时失去了抗污染能力,相比之下POEGMA接枝膜的特性得到了保持。采用紫外光辐照接枝聚合方法构建了PSBMA/POEGMA共混接枝改性膜,该膜呈现了良好的离子响应,随着盐离子浓度的增加,其通量会大幅度下降。在相同盐离子浓度溶液中,改性膜表面PSBMA链段含量的提高,该膜对离子的响应性也会随之增加。
[Abstract]:Surface pollution is a common Ceekay disease in the biomedical materials, marine operation and membrane separation technology. The common method to solve the problem is to construct the antifouling surface. At present, the amphoteric ion polymers (PEG) and polysulfonic acid betaine (PSBMA) are the two most commonly used antifouling materials for hydrophilic modification. The purpose of this paper is to explore the simple and effective anti pollution surface construction method by using the super high hydrophilicity of PSBMA and PEG, and compare the anti pollution and stability of the two kinds of polymer modified coatings. The specific research work focuses on the following aspects: using the wire mesh as the mold surface, the selection of PSBMA as the anti pollution material and the more The PSBMA'is modified on the surface by the oxidation of dopamine in the alkaline solution and the excellent adhesion force. XPS and FESEM are used to characterize the morphology and composition of the steel wire mesh. The.PSBMA/PDA modified steel wire mesh has the characteristics of underwater super oil and anti oil adhesion, and the contact angle of the underwater oil can be increased to 15. 8.6 + 8 degrees, while the rolling angle is only 3.9 degrees. At the same time, the coating remains stable in the organic solvent and seawater for a long time. The PSBMA/PDA modified surface is constructed by the same method for polypropylene microporous membrane (PPMM). The modified membrane is highly hydrophilic in the test of water contact angle and flux, and is also endowed with excellent anti protein absorption on the surface of the membrane. Performance. But PEG does not apply to the same co deposition method. With the increase of PEG concentration, the surface deposition density will decrease greatly. The surface of the constructed surface is strongly adsorbed on bovine serum albumin (BSA), indicating that the modified coating constructed by PEG/PDA co deposition does not have the anti pollution properties. Natural polyphenol tannic acid (TA) is used as a method. The assembly unit was used to compare the LBL assembly process of the above polymer. The assembly process was monitored with the UV absorption spectrum and QCM. The chemical composition and morphology of the assembly layer were characterized by FT-IR/MR, XPS, VASE and AFM. The results showed that the electrostatic interaction between PSBMA and TA was formed and the surface could be in a solution between pH 4-10. In contrast, the assembly driving force of PEG and TA is weak hydrogen bond interaction, and its growth conforms to the exponential growth curve, but the coating is decomposed and eluted under the alkaline solution. At the same time, (PSBMA/TA) n, three model protein BSA, Lys (Lys) and blood red can be obtained with good anti protein adsorption effect on the surface. The adsorption of protein (Hgb) was reduced to 328357, and and 509 ng/cm2. was graft polymerization of SBMA and OEGMA on the surface of PPMM by UV irradiation grafting polymerization. The obtained two modified membranes all had high hydrophilicity and good protein adsorption resistance. But they were dissolved in H2O2/Cu2+ and NaCIO. The oxidation stability in the liquid is different.FT-IR/ATR, and the results of XPS and TOF-SIM show that the degradation rate of PSBMA is greater than that of POEGMA. The hydrolysis of ester bond and the departure of sulfonic acid betaine are mainly occurred. After oxidative degradation, the water contact angle of the PSBMA graft film increases from 36 to 110 degrees, and the anti pollution ability is lost, compared with the POEGMA graft membrane. The properties of PSBMA/POEGMA were maintained. The graft copolymerization membrane was constructed by UV irradiation graft polymerization. The membrane presented a good ionic response. With the increase of salt ion concentration, the flux would decrease greatly. In the same salt ion concentration solution, the content of the PSBMA chain section on the surface of the modified membrane was improved. Responsiveness will also increase.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB306
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本文编号：2053331