本文關(guān)鍵詞： 聚丙烯腈 點擊化學(xué) 烷基化反應(yīng) 超濾膜 膜蒸餾　出處：《天津工業(yè)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：聚丙烯腈(PAN)具有良好的耐溶劑性、化學(xué)穩(wěn)定性和熱穩(wěn)定性,可以通過非溶劑誘導(dǎo)相轉(zhuǎn)化方法進行加工成膜,且成膜性好,因此是一種常用的膜材料。但PAN膜的親疏水適中,這使其在水處理的膜過濾和膜接觸器中應(yīng)用都存在較為嚴重的膜污染和膜浸潤現(xiàn)象,從而限制了膜分離效率和膜的使用壽命。對PAN膜進行改性,以強化其親水和疏水性能,使其能更好地滿足不同形式的膜法水處理應(yīng)用需求,是PAN膜需要重點突破的方向。點擊化學(xué)方法操作簡單、條件溫和且轉(zhuǎn)化率高,廣泛應(yīng)用于高分子合成及有機膜化學(xué)改性。針對水處理膜過濾過程中超濾膜通量低、抗污染性差的問題,本文通過點擊化學(xué)實現(xiàn)環(huán)加成反應(yīng)合成含1,2,3,4-四氮唑的親水性聚丙烯腈共聚物(TZ-PAN),并以TZ-PAN與碘甲烷進行烷基化反應(yīng)得到MTZ-PAN共聚物。通過控制反應(yīng)時間(5min-120min)可以調(diào)控TZ-PAN和MTZ-PAN功能化程度(DF)為5%-16%。以相轉(zhuǎn)化法制備TZ-PAN和MTZ-PAN平板膜,膜測試結(jié)果顯示,隨著1,2,3,4-四氮唑基團含量的增加TZ-PAN超濾膜接觸角由63°降低到52°,水通量由111OL/(m2·h·bar)提高到715L/m2·h·bar),并對蛋白質(zhì)溶液所造成的膜污染表現(xiàn)出更高的水利清洗可逆性,水通量恢復(fù)率為90%。烷基化處理后,超濾膜的機械性能極大增強,對于功能化程度為16%的MTZ-PAN膜,其斷鏈伸長率增加至21%,但接觸角升高到71°,水通量降低到242L/(m2·h·bar),BSA截留率仍保持在80%。通過點擊化學(xué)和烷基化反應(yīng)可以有效地調(diào)控PAN膜的親水性,從而改善PAN超濾膜的純水通量和抗污染性能。為進一步驗證烷基鏈長度對PAN平板膜性能的影響,將癸烷和十六烷基分別通過烷基化反應(yīng)引入到TZ-PAN共聚物中,DF為10%和20%。相轉(zhuǎn)化制備TZ-PAN-癸烷和TZ-PAN-十六烷微孔膜在烷基鏈作用下具有較強的疏水性,且隨著脂肪鏈長度和功能化程度的增加,制得的平板膜接觸角逐步升高。當(dāng)DF為20%時,TZ-PAN-癸烷膜的接觸角為101°,TZ-PAN-十六烷膜的接觸角為104°。將疏水改性PAN膜應(yīng)用于直接接觸膜蒸餾系統(tǒng),對35g/LNaCl溶液進行脫鹽處理,實驗結(jié)果表明,隨著料液溫度的增加(50-80℃)TZ-PAN-十六烷疏水膜的膜蒸餾通量由3kg/(m2·h)提升至12kg/(m2·h),但分離因子仍小于1。相同功能化程度下,TZ-PAN-癸烷的膜蒸餾效果與TZ-PAN-十六烷相差不大。通過引入烷基鏈(癸烷和十六烷)可以有效提高PAN平板膜的疏水性,從而改善PAN膜的膜蒸餾的運行效果。
[Abstract]:Polyacrylonitrile (pan) has good solvent resistance, chemical stability and thermal stability. It can be processed by non-solvent induced phase transformation method and has good film-forming property, so it is a commonly used membrane material, but the hydrophobic property of PAN membrane is moderate. As a result, the membrane fouling and membrane soaking in water treatment membrane filtration and membrane contactor are very serious, which limits the membrane separation efficiency and membrane service life. The PAN membrane is modified to enhance its hydrophilicity and hydrophobicity. It is a key breakthrough direction for PAN membrane to meet the application requirements of different forms of membrane water treatment. The click-chemical method is easy to operate, mild conditions and high conversion rate. It is widely used in polymer synthesis and organic membrane chemical modification. In the process of water treatment membrane filtration, the flux of ultrafiltration membrane is low and the resistance to pollution is poor. In this paper, the hydrophilic polyacrylonitrile copolymers (TZ-PANN) containing 1o 2N 3N 4- tetrazole were synthesized by click-chemical cycloaddition reaction. The MTZ-PAN copolymers were prepared by alkylation of TZ-PAN with methyl iodide. By controlling the reaction time of 5 min-120 mins, the TZ-PAN and TZ-PAN copolymers could be controlled. The degree of MTZ-PAN functionalization was 5- 16.The TZ-PAN and MTZ-PAN flat films were prepared by phase inversion method. The results of membrane test showed that the contact angle of TZ-PAN ultrafiltration membrane decreased from 63 擄to 52 擄, and the water flux increased from 111 OLP / m 2 路h 路h 路barr to 715L / m 2 路h 路barg with the increase of the content of 1 ~ 2 ~ 2 ~ 3 ~ 3 ~ 3 ~ (-) -tetrazolium. The membrane fouling caused by protein solution showed a higher reversibility to water conservancy cleaning, and the water flux increased from 111OLR / m ~ 2 路h 路barp to 715L / m ~ 2 路h 路barge. The recovery rate of water flux is 90. After alkylation, the mechanical properties of ultrafiltration membrane are greatly enhanced. For MTZ-PAN membrane with functionalized degree of 16%, The elongation at break chain increased to 21, but the contact angle increased to 71 擄, and the water flux decreased to 242 L / m 2 路h 路h 路barbaron. The retention rate of BSA remained at 80%. The hydrophilicity of PAN membrane could be effectively regulated by click-chemical and alkylation reactions. In order to improve the pure water flux and antifouling performance of PAN ultrafiltration membrane, the effect of alkyl chain length on the performance of PAN flat membrane was further verified. Decane and cetyl were introduced into TZ-PAN copolymers by alkylation reaction. The phase conversion of TZ-PAN- decane and TZ-PAN- cetane microporous membranes had strong hydrophobicity under the action of alkyl chain. With the increase of the length of fat chain and the degree of functionalization, the contact angle of TZ-PAN- decane membrane increased gradually. When DF was 20, the contact angle of TZ-PAN- decane membrane was 101 擄and the contact angle of TZ-PAN- cetane membrane was 104 擄. Hydrophobic modified PAN membrane was applied to direct contact membrane distillation system. The desalination of 35g / L NaCl solution shows that, The membrane distillation flux of TZ-PAN- cetane hydrophobic membrane increased from 3 kg / m ~ 2 路h to 12 kg / m ~ 2 路h ~ (-1) with the increase of feed temperature, but the separation factor was still less than 1. The effect of membrane distillation of TZ-PAN- decane was similar to that of TZ-PAN- hexadecane at the same degree of functionalization. The effect of membrane distillation was similar to that of TZ-PAN- hexadecane by introducing TZ-PAN- hexadecane. Alkyl chain (decane and cetane) can effectively improve the hydrophobicity of PAN flat membrane. Thus, the operation effect of membrane distillation of PAN membrane was improved.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ051.893

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