發(fā)布時間：2018-06-22 15:49

  本文選題：抗污染表面 + 聚磺酸甜菜堿��； 參考：《浙江大學(xué)》2015年博士論文

【摘要】：表面污染在生物醫(yī)用材料、海洋作業(yè)和膜分離技術(shù)領(lǐng)域中是普遍存在的沉珂頑疾。解決的常用方法就是構(gòu)建抗污染表面。目前,聚乙二醇(PEG)和以聚磺酸甜菜堿(PSBMA)為例的兩性離子聚合物是最為常用的兩種用于親水化改性的抗污染材料。本論文旨在利用PSBMA和PEG超高的親水性,探究簡便有效的抗污染表面構(gòu)建方法,并比較兩種聚合物改性涂層的抗污染性和穩(wěn)定性。具體研究工作主要圍繞以下幾個方面展開：采用鋼絲網(wǎng)作為模型表面,選用PSBMA作為抗污染材料與多巴胺混合,通過多巴胺在堿性溶液中的氧化自聚和優(yōu)異的粘附力將PSBMA'修飾在表面。借助XPS和FESEM等分析手段表征改性前后鋼絲網(wǎng)的形貌與組成變化。PSBMA/PDA改性鋼絲網(wǎng)具有水下超疏油與抗油滴粘附特性,其水下油接觸角可以提高至158.6±8.0°,而滾動角只有3.9°。同時,涂層在有機(jī)溶劑和海水長時間浸泡下依然保持穩(wěn)定。采用相同方法為聚丙烯微孔膜(PPMM)構(gòu)建了PSBMA/PDA改性表面。改性膜在水接觸角和通量測試中表現(xiàn)出極強(qiáng)的親水化,也賦予膜表面優(yōu)異的抗蛋白質(zhì)吸附性能。但是PEG并不適用于相同的共沉積方法。隨著PEG濃度的提高,表面沉積密度會大幅度下降,所構(gòu)建的表面對牛血清白蛋白(BSA)具有極強(qiáng)的吸附,說明通過PEG/PDA共沉積構(gòu)建的改性涂層并不具有抗污染性能。以天然多酚單寧酸(TA)作為組裝單元,用以研究比較上述聚合物的LBL組裝過程。借助紫光吸收光譜和QCM來監(jiān)測組裝過程,采用FT-IR/MR、XPS、VASE以及AFM對組裝層的化學(xué)組成與形貌進(jìn)行表征。結(jié)果表明PSBMA和TA之間會形成靜電相互作用,使得表面可以在pH 4-10之間的溶液以及鹽溶液中保持穩(wěn)定。相比之下,PEG和TA的組裝驅(qū)動力是弱的氫鍵相互作用,其增長符合指數(shù)型增長曲線,但涂層在堿性溶液下就分解洗脫。同時,(PSBMA/TA)n;表面具有良好的抗蛋白質(zhì)吸附效果,可以將三種模型蛋白BSA、溶菌酶(Lys)和血紅蛋白(Hgb)的吸附量降低至328,357, and 509 ng/cm2。采用紫外光輻照接枝聚合方法實(shí)現(xiàn)了SBMA和甲基丙烯酸聚乙二醇酯(OEGMA)在PPMM表面的接枝聚合,所獲得的兩種改性膜都具有高的親水性和良好的抗蛋白質(zhì)吸附性能。但它們在H2O2/Cu2+和NaCIO溶液中的氧化穩(wěn)定性卻大為不同。FT-IR/ATR、XPS和TOF-SIM結(jié)果表明PSBMA的降解速率要大于POEGMA,主要發(fā)生了酯鍵的水解和磺酸甜菜堿的離去。經(jīng)過氧化降解,PSBMA接枝膜的水接觸角從36°增加到110°,同時失去了抗污染能力,相比之下POEGMA接枝膜的特性得到了保持。采用紫外光輻照接枝聚合方法構(gòu)建了PSBMA/POEGMA共混接枝改性膜,該膜呈現(xiàn)了良好的離子響應(yīng),隨著鹽離子濃度的增加,其通量會大幅度下降。在相同鹽離子濃度溶液中,改性膜表面PSBMA鏈段含量的提高,該膜對離子的響應(yīng)性也會隨之增加。
[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.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB306
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本文編號：2053331