本文選題：苯硼酸 + 聚乙烯醇　； 參考：《江南大學(xué)》2017年碩士論文

【摘要】：含硼酸官能團(tuán)類化合物,自從被發(fā)現(xiàn)能與1,2-二醇或1,3-二醇形成可逆的硼酸酯以來,在各研究領(lǐng)域都得到了廣泛的關(guān)注。尤其是對(duì)于含苯硼酸官能團(tuán)類化合物的復(fù)合材料的研究,即利用苯硼酸優(yōu)異的性能與其他材料復(fù)合,從而賦予新材料某些優(yōu)秀的性能。由于自組裝技術(shù)具有操作簡便,成膜不受基材的限制,驅(qū)動(dòng)力多種多樣等特點(diǎn),使其在材料改性方面得到了廣泛的研究。本論文以硼酸多醇相互作用為驅(qū)動(dòng)力,在纖維素膜表面進(jìn)行了自組裝研究,主要研究內(nèi)容由以下三部分組成:1.硼酸改性纖維素膜的制備、表征及性能分析采用2,2,6,6-四甲基哌啶-1-氧基(TEMPO)氧化法及酰胺化反應(yīng)在纖維素膜表面接枝上了苯硼酸官能團(tuán)。利用紅外光譜法和熒光法對(duì)改性纖維素膜進(jìn)行了表征;利用抗張?jiān)囼?yàn)機(jī)和耐破度儀對(duì)改性纖維素膜的機(jī)械性能進(jìn)行了測試;最后探索了改性纖維素膜對(duì)表面含有多醇結(jié)構(gòu)的微球吸附與解吸附性能,結(jié)果表明:當(dāng)TEMPO、NaBr和10 wt%的NaClO溶液的用量分別為0.05 g、0.025 g、4 mL,氧化時(shí)間為45 min時(shí),可以獲得機(jī)械性能較佳的改性纖維素膜,該纖維素膜對(duì)含有多醇結(jié)構(gòu)微球的吸附與解吸過程具有pH可控性。2.硼酸改性棕櫚蠟乳液微球在纖維素膜上的自組裝研究通過控制棕櫚蠟(CW)的濃度、均質(zhì)速度及均質(zhì)時(shí)間制備出粒徑較小,分散均勻的棕櫚蠟乳液,經(jīng)3-氨基苯硼酸(ABBA)改性后得到表面接枝有苯硼酸官能團(tuán)的乳液顆粒(CW-ABBA),之后以CW-ABBA和聚乙烯醇(PVA)為組裝單元,在纖維素膜表面組裝上一對(duì)PVA/CW-ABBA的高分子膜。復(fù)合膜的比表面能低,成膜性好,與纖維素的結(jié)合力較強(qiáng),有效的改善了纖維素膜的水蒸氣阻隔、拒水及機(jī)械性能。結(jié)果表明,PVA與CW-ABBA的組裝過程具有pH可控性,最佳組裝pH值為10.5,在該條件下進(jìn)行PVA/CW-ABBA組裝處理后的纖維素膜的水蒸氣透過率下降了24.2%,拒水性能提高了60.2%,抗張指數(shù)提高了61.9%,伸長率提高了0.4倍,而且基本保持了原纖維素膜的熱穩(wěn)定性。3.Chitosan-PBA/PVA、PVAm-PBA/PVA多層組裝薄膜的制備通過酰胺化反應(yīng)將4-羧基苯硼酸(PBA)接枝到殼聚糖(Chitosan)和聚乙烯胺(PVAm)的主鏈上,得到Chitosan-PBA和PVAm-PBA,接著將它們和聚乙烯醇(PVA)作為組裝單元,在纖維素膜上進(jìn)行層層自組裝,得到Chitosan-PBA/PVA、PVAm-PBA/PVA多層組裝薄膜改性的纖維素膜,同時(shí),以硅片和聚乙烯微球?yàn)槟Ｐ臀锾接懥烁叻肿訉?duì)的組裝過程。利用橢圓光偏振儀對(duì)組裝過程中的膜層厚度變化進(jìn)行了表征;通過電位分析儀對(duì)組裝過程中微球表面的電荷變化情況進(jìn)行了測試;利用光學(xué)輪廓儀對(duì)高分子膜層的均勻性和表面粗糙度進(jìn)行了追蹤;通過抗張?jiān)囼?yàn)機(jī)對(duì)改性纖維素膜的機(jī)械性能進(jìn)行了測試;最后探索了改性纖維素膜對(duì)表面含有多醇結(jié)構(gòu)的微球吸附與解吸附性能。結(jié)果表明:pH對(duì)Chitosan-PBA、PVAm-PBA與PVA之間的相互作用具有影響,在pH 4.5下,聚合物的膜層厚度不隨著沉積次數(shù)的增加而變化;在pH 5.5-10.5范圍內(nèi),高分子組裝薄膜厚度隨著組裝溶液pH的升高呈現(xiàn)先增加后趨于穩(wěn)定的趨勢(shì);在相同pH下,Chitosan-PBA/PVA組裝對(duì)的單層薄膜厚度高于PVAm-PBA/PVA。微球表面的電泳變化顯示Chitosan-PBA、PVAm-PBA與PVA組裝過程中的電勢(shì)隨著組裝次數(shù)的增加呈現(xiàn)有規(guī)律的多邊形線性變化,且Chitosan-PBA/PVA組裝對(duì)的電勢(shì)變化幅度高于PVAm-PBA/PVA組裝對(duì);光學(xué)輪廓儀測試表明,不同pH下組裝有相同高分子對(duì)數(shù)的硅板表面的粗糙度隨著pH值的增加而逐步增加,而且相對(duì)而言PVAm-PBA/PVA組裝對(duì)的平滑度更高;機(jī)械性能測試表明Chitosan-PBA/PVA和PVAm-PBA/PVA對(duì)纖維素膜的機(jī)械性能的提高具有積極的作用,其中,PVAm-PBA/PVA的增強(qiáng)效果優(yōu)于Chitosan-PBA/PVA并且在pH 9.5下具有最佳的增強(qiáng)效果。當(dāng)纖維素膜表面組裝上30對(duì)PVAm-PBA/PVA時(shí),纖維素膜的抗張指數(shù)和伸長率分別提高了53%和76%。掃描電子顯微鏡表明改性纖維素膜對(duì)含有多醇結(jié)構(gòu)微球的吸附與解吸過程具有pH可控性。此外,熱重分析表明PVAm-PBA/PVA改性的纖維素膜的熱穩(wěn)定略好于Chitosan-PBA/PVA改性的纖維素膜。
[Abstract]:Boric acid functional group compounds have attracted wide attention since they were found to be able to form reversible borate esters with 1,2- or 1,3- diols. Especially, the study of composite materials containing benzyl boric acid functional group compounds, that is, the excellent properties of benzyl boric acid are combined with other materials to give new materials. In this paper, the self assembly of the boric acid polyol interaction is used as the driving force. The main research contents are as follows. The three part consists of the preparation, characterization and performance analysis of 1. boracic acid modified cellulose membrane. The 2,2,6,6- four methyl piperidine -1- oxygen (TEMPO) oxidation and amidation were used to graft the benzboric acid functional groups on the surface of the cellulose membrane. The modified fibrin membrane was characterized by infrared spectroscopy and fluorescence; the tensile test machine and the resistance to rupture were used. The mechanical properties of the modified cellulose membrane were tested by the degree meter. At last, the adsorption and desorption properties of the modified cellulose membrane on the surface containing polyol structure were explored. The results showed that the mechanical properties of TEMPO, NaBr and 10 wt% NaClO solutions were 0.05 g, 0.025 g, 4 mL and 45 min, and the mechanical properties were better. The modified cellulose membrane has pH controllability for the adsorption and desorption process of polyol structure microspheres, and the self-assembly of.2. boric acid modified palm wax microspheres on the cellulose membrane by controlling the concentration of the palm wax (CW) by controlling the concentration of the palm wax (CW), the homogenization time and the homogenization time for the preparation of the palm wax emulsion with small particle size and uniform dispersion, through 3- ammonia After modification of benzboric acid (ABBA), the surface grafting of the emulsion particles (CW-ABBA) with benzboric acid functional group was obtained, and then a pair of PVA/CW-ABBA polymer membrane was assembled on the surface of cellulose membrane with CW-ABBA and polyvinyl alcohol (PVA) as assembly unit. The composite film has a lower surface energy, better film forming, stronger binding force with cellulose, and effective improvement of fiber. The water vapor barrier, water repellency and mechanical properties of the vitamin film show that the assembly process of PVA and CW-ABBA has pH controllability and the optimum assembly pH value is 10.5. The water vapor transmission rate of the cellulose membrane after PVA/CW-ABBA assembly treatment under this condition is 24.2%, the water repellent performance is increased by 60.2%, the tensile index is increased by 61.9%, and the elongation rate is raised. It was 0.4 times higher and basically maintained the thermal stability of the original cellulose membrane.3.Chitosan-PBA/PVA, and the preparation of PVAm-PBA/PVA multilayer assembly films by amidation of 4- carboxylic benzyl boric acid (PBA) onto the main chain of chitosan (Chitosan) and polyvinyl amine (PVAm), obtained Chitosan-PBA and PVAm-PBA, followed by them and polyvinyl alcohol (PVA). For the assembly unit, the layers of cellulose films are self assembled on the cellulose membrane to obtain the modified cellulose films of Chitosan-PBA/PVA and PVAm-PBA/PVA multilayer assembly films. At the same time, the assembly process of the polymer pairs is discussed with silicon and polyethylene microspheres as models. The change of the thickness of the film layer in the process of the assembly process is characterized by the elliptical polarizer; The charge change of the surface of the microspheres during the assembly process was tested by the potential analyzer, the uniformity and the surface roughness of the polymer film were traced by the optical profilometer, and the mechanical properties of the modified cellulose membrane were tested by the tensile test machine. Finally, the surface of the modified cellulose membrane was found to contain polyol knots on the surface. The results show that pH has an effect on the interaction between Chitosan-PBA, PVAm-PBA and PVA. At pH 4.5, the film thickness of the polymer does not change with the increase of the deposition times. In the range of pH 5.5-10.5, the thickness of the polymer film is increased with the increase of the pH in the assembly solution, and then tends to increase. The trend of stability is that under the same pH, the electrophoretic change of the layer thickness of the Chitosan-PBA/PVA assembled monolayer is higher than that of the PVAm-PBA/PVA. microsphere, and the potential of the electromotive force in the assembly process of PVAm-PBA and PVA exhibits a regular polygon linear change with the increase of the number of assembly, and the potential of the potential of the Chitosan-PBA/PVA assembly is high. The optical profilometer test shows that the roughness of the surface of the silicon plate with the same polymer logarithm under different pH increases with the increase of pH value, and the smoothness of the PVAm-PBA/PVA assembly pair is higher relatively; the mechanical properties test shows the mechanical properties of Chitosan-PBA/PVA and PVAm-PBA/PVA on the cellulose membrane. The enhancement of energy has a positive effect. Among them, the enhancement effect of PVAm-PBA/PVA is better than that of Chitosan-PBA/PVA and has the best enhancement effect under pH 9.5. When the surface of the cellulose membrane is assembled with 30 pairs of PVAm-PBA/PVA, the tensile index and elongation of the cellulose membrane are increased by 53% and 76 respectively. The adsorption and desorption process with polyol structure microspheres has pH controllability. In addition, TG analysis shows that the thermal stability of PVAm-PBA/PVA modified cellulose membrane is better than that of Chitosan-PBA/PVA modified cellulose membrane.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O636.11

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