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随着经济的快速发展以及人们对环境重视程度的提高，聚砜膜分离技术以其高效、节能、环保、选择性高、装置灵活等特点，在工农业水处理、海水淡化、生物医学等方面有着广泛的应用。聚砜由于其耐酸碱腐蚀，抗氧化能力强，具有优良的力学性能，适合在压力环境下使用，常被用于膜分离材料。但由于聚砜材料自身亲水性差，膜分离过程中，生物悬浮物或大分子/胶体沉积易在膜表面和膜孔内部造成膜污染。此外，聚砜质脆，柔韧性较差的缺点也限制了其在其他领域的应用。 本文针对聚砜树脂柔韧性不足、亲水性差的问题，通过羟基封端的聚砜和异氰酸酯基封端的聚氨酯预聚体共聚制备聚氨酯改性聚砜树脂，结合聚氨酯的结构特性，改善聚砜树脂柔韧性和亲水性。论文主要包括以下内容：制备了以羟基封端的聚砜，得到一系列不同分子量聚砜，研究了该合成方法的最佳合成条件及影响因素；合成了以异氰酸酯（NCO）基团封端的聚氨酯预聚体；用羟基封端的聚砜和聚氨酯预聚体共聚，合成了聚氨酯改性聚砜（PSF-PU）树脂，研究了其制备的最佳条件；利用 ATR-IR、1HNMR、GPC手段对聚氨酯改性聚砜树脂的结构进行了表征；将改性的聚砜树脂制备成膜，测试该膜材料的断裂伸长率、抗张强度、表面接触角，玻璃化转变温度等物理性能；将改性的聚砜树脂制备成平板超滤膜，测定超滤膜的纯水通量以及对PEG-10000分子的截留率等分离性能。再用牛血清蛋白模拟动态吸附，测试超滤膜在使用过程中的抗污染性。 通过调节聚砜以及聚氨酯改性聚砜树脂的制备条件，研究各因素的影响，确定聚砜的合成最佳条件为：反应单体浓度40%，甲苯用量35 mL，带水时间2 h，缩聚反应温度160℃，时间4 h。聚氨酯改性聚砜树脂的最佳合成条件为：反应温度80℃，时间6 h；反应物浓度25%。 ATR-IR、1HNMR、GPC分析表明，聚砜的端羟基与聚氨酯预聚体的端异氰酸酯基发生了反应，聚氨酯预聚体与聚砜发生反应，具有聚氨酯特性的链段成功引入到聚砜上。 聚氨酯改性聚砜树脂膜的玻璃化转变温度为188.33℃，比聚砜高2.75℃；断裂伸长率为18.62%，比聚砜膜高4.38%；水接触角比聚砜小21.5° ~ 22.3°，亲水性得到提高。 聚氨酯改性聚砜树脂超滤膜的纯水通量增加4.36 mL•cm-2•h-1，对于PEG-10000分子的截留率提高4%，分离性能提高；对牛血清蛋白的总污染度减小0.18389，不可逆污染减小减少0.12243，抗污染性能提高。 将聚氨酯改性聚砜树脂超滤膜和聚砜超滤膜处理皮革脱毛废水测定超滤膜对废水中的硫化物、COD、色度、悬浮物及灰分的截留率。测定结果表明聚氨酯改性聚砜树脂超滤膜相比聚砜超滤膜对于皮革脱毛废水中的各项指标均有较高的截留率。 Because of the rapid economic development and the continuous improvement of people's attention to the environment, polysulfone separation membrane technology, depending on its high efficiency, energy saving, environmental protection, high selectivity and device flexibility, has been widely used in the industrial and agricultural water treatment, desalination, biomedical applications and so on. Due to its acid and base resistance, anti-oxidation ability, excellent mechanical properties, adaptability for using under pressure, polysulfone was always selected for membrane material. However, hydrophilicity of polysulfone was poor, which could easily result in the membrane fouling from biological suspended solids or macromolecules/colloids deposited on the membrane surface and membrane inner holes. Besides, the application of polysulfone material in other fields is limited as its brittleness and poor flexibility. In this thesis, in order to improve hydrophilicity and flexibility of polysulfone resin, firstly, the synthesis of hydrophilic isocyanate group ended polyurethane and the hydroxyl ended polysulfone was carried out. Then the copolymerization of the hydroxyl ended polysulfone and the isocyanate group ended polyurethane was carried out. The preparation method, the optimum preparation conditions and influence factors of polysulfone and polyurethane modified polysulfone resin were studied by comparing the viscosity of the products. The structures of polyurethane modified polysulfone resin was characterized with ATR-IR, 1HNMR and GPC. The polyurethane modified polysulfone membrane resin membrane was prepared through L-S phase inversion method. The elongation at break, tensile strength contact angle, the glass transition temperature and other physical properties of modified membrane was tested. The polyurethane modified polysulfone resin ultrafiltration membrane was prepared. The pure water flux and the reject rate of the PPG-10000 of the ultrafiltration membrane were tested through the ultrafiltration cup. The antifouling property was tested by assessing the flux loss of bovine serum albumin in the process of dynamic adsorption. We studied the preparation conditions of polysulfone . Finally, we found that the monomer concentration was 40%, the dosage of toluene was 35 mL, the dewater time was 2 h, condensation reaction temperature was 160℃ and condensation reaction time was 4 h. The best copolymerization temperature of polysulfone and polyurethane copolymerization was 80℃; The best copolymerization time was 6 h; The best copolymerization concentration was 25%. Tg of polyurethane modified polysulfone resin membrane was 188.33℃, which was 2.75℃ higher than the polysulfone. Elongation at break of polyurethane modified polysulfone membrane was 18.62%, 4.38% higher than the polysulfone membrane. The water contact angle of polyurethane modified polysulfone membrane are 21.5°~22.3° lower than polysulfone membrane. The pure water flux of polyurethane modified polysulfone resin ultrafiltration membrane was 4.36 mL•cm-2•h-1 higher than polysulfone membrane and the reject rate was 4% higher than polysulfone membrane. The pollution resistance performance of polyurethane modified polysulfone ultrafiltration membrane was better than polysulfone ultrafiltration membrane. Total pollution reduced by 0.18389, irreversible pollution reduced by 0.12243. When we used the flat ultrafiltration membrane for treating laboratory leather unhairing waste-water, the application performance of the flat ultrafiltration membrane was assessed by comparing the chroma, ash content, sulfide, suspended solids, chemical oxygen demand (COD) between influent and effluent. We found that the reject rate of COD, sulfide, chroma, suspended solids and ash treated by polyurethane modified polysulfone resin ultrafiltration membrane were higher than by polysulfone ultrafiltration membrane. |
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爱与雨下: 金币+1 2014-06-10 19:03:37
supee: 金币+50, 翻译EPI+1, ★有帮助, 改得可以 如果重新把全文翻译一遍就不错了 谢谢 2014-06-10 19:18:47
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supee: 金币+50, 翻译EPI+1, ★有帮助, 改得可以 如果重新把全文翻译一遍就不错了 谢谢 2014-06-10 19:18:47
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修改后的文章： 第一段： With the rapid development of economy and the increasing attention people pay on the environment, the separation technology of polysulfone membrane depending on its high efficiency, energy saving, environmental protection, high selectivity and device flexibility, has been widely used in the water treatment of the industrial and agricultural, desalination, biomedical applications and so on. Due to its acid and alkali resistance, anti-oxidation ability, excellent mechanical properties, fitness for using under pressure, polysulfone is always selected as the material of membrane. However, the poor hydrophilicity of polysulfone could easily result in the membrane fouling from biological suspended solids or macromolecules/colloids deposited on the membrane surface and membrane inner holes. Besides, the brittleness and poor flexibility of polysulfone material has limited its application in other fields. |
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