【作者】 王勇；

【导师】 王鸿儒；

【作者基本信息】 陕西科技大学 ， 皮革化学与工程， 2012， 硕士

【摘要】 聚砜类树脂是指由芳环、砜基和醚基构成大分子主链的一类热塑性高分子材料,其芳环赋予了材料的刚性,砜基的存在使得材料有着优异的耐热性和抗氧化性,醚基则加强了材料的成型加工性能。由于这种独特的分子结构,使得聚砜类材料耐水解、耐酸碱腐蚀、耐热性能优异,且具有良好的物理机械强度,广泛应用于超滤、纳滤、气体分离等领域,在分离膜市场占有主导地位。双酚A型聚砜是聚砜类树脂中应用最为广泛的一种,但是它在耐溶剂性方面并不好,而且其材料的韧性较差,致使它的应用范围受到了一定的限制。聚醚醚砜树脂的韧性和耐溶剂性能都较好。因此,本课题以共聚的方法,在聚砜的分子主链中引入聚醚醚砜链段,以提高聚砜类树脂的耐溶剂性,增强其材料的韧性,并且将其合成的产物制备成超滤膜,应用于染色加脂废水的处理,在实验室阶段探讨了膜分离技术浓缩和回收废水中加脂剂和染料等物质的可能性。实验以双酚A (Bi s-A).对苯二酚(HQ)与4,4’-二氯二苯砜(DCS)为反应单体,进行溶液缩聚反应,合成出了Bis-A/HQ/DCS共聚物。利用红外光谱(FT IR)、核磁共振氢谱(1H-NMR)表征了共聚物的链结构；采用示差扫描量热分析(DSC)和热重分析(TG)对共聚物的热性能进行了分析。同时,用不同的溶剂溶解聚合产物,考察了产物的耐溶剂性能。结果表明,聚醚醚砜链段的引入能够改善聚砜树脂的抗溶剂性能,同时聚砜材料的耐热性能也得到了提高。探讨了合成过程中反应条件对产物性能的影响,结果发现在高初始单体浓度下合成的产物有着较高的分子量,其产率也很高；选择无水碳酸钾具有最好的催化效果,而且用适量的水溶解碳酸钾能够提高其活性,促进酚氧盐的形成,提高了聚合反应速度。采用相转化法将双酚A型聚砜聚合物和Bis-A/HQ/DCS共聚物制备成超滤膜。对超滤膜的流通量和截留率等指标进行了分析,同时通过表面接触角的测量考查了超滤膜的亲水性。用扫描电镜对超滤膜的微观形貌和断面结构进行了观察。对超滤膜的物理机械强度也进行了测试。结果表明,Bis-A/HQ/DCS共聚物制备的超滤膜较双酚-A型聚砜聚合物超滤膜有着更好的亲水性,分离性能非常好；膜的电镜图表明超滤膜表面有着细小的微孔,断面结构为很薄的致密的皮层与疏松的海绵状的支撑层。将超滤膜应用于染色加脂废水的回收利用,探讨了不同操作条件对超滤的影响。超滤结果表明,在最佳条件下,废水中的悬浮物、色度、总氮、总固含量和COD分别下降了100%、96.2%、86.6%、96.4%和91.8%。污染后的超滤膜经过清洗液(pH=10)清洗后,膜的流通量能够恢复96%。超滤后的浓缩液能再回用于染色加脂工序。此方法能够节省30%的染料和加脂剂,渗透液能够再用于鞣制前的浸酸工序。采用浓缩液进行染色加脂所得皮革与传统工艺相比,物理机械性能非常接近。用超滤的方法处理废水,降低了制革废水对环境的影响,简化了废水的处理,节省了化料和水。更多还原

【Abstract】 Polysulfones resin is a thermoplastic polymer materials, the main chain of polysulfones macromolecule consists of aromatic ring, sulfone, and ether. The rigidity of the material is provided by aromatic ring, the excellent resistance to heat and oxidation is supported by sulfone group, and the processing behavior of materials is strengthened by ether group. Because of this unique molecular structure, the polysulfones material has excellent mechanical strength and good resistance to hydrolysis, heat, acid and alkali. Polysulfones materials are widely used in ultrafiltration, nanofiltration, gas separation, and occupy an important place in the membranes market.As the most widely used polysulfone resin, bisphenol-A(Bis-A) polysulfone has poor resistance to solvent, and the toughness of material is also poor, these results in the application limitations of materials. Poly ether ether sulfone(PEES) resin has good toughness and solvent resistance. In order to improve the solvent resistance of polysulfone and the toughness of the material, the PEES segments was introduced to polysulfone main chain by copolymerization in this paper, and the synthetic copolymers were made into ultrafiltration membrane, and the membrane was used to treat the dyeing-fatliquoring effluents. The possibility of recovering and concentrating dyes and fatliquoring materials through membrane process was investigated on the laboratory scale.In this study, the Bis-A/HQ/DCS copolymers were synthesized by nucleophilic polycondensation of bisphenol-A (Bis-A), hydroquinone (HQ) with4,4’-dichloro-diphenyl sulfone (DCS). The structure of copolymer was characterized by Infrared Spectroscopy (FT-IR) and Proton Nuclear Magnetic Resonance Spectroscopy (’H-NMR); the thermal properties of the copolymer was analyzed by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric (TG). The solvent resistance of the product was investigated by dissolving the polymers with different solvents. The results showed that the resistance to solvent and heat of polysulfone resin was improved by introducing polyether ether sulfone segments into polysulfone.The effect of the reaction conditions on the performance of the product had been discussed. The results showed that the synthetic product with higher molecular weight and the higher yield could be achieved by increasing initial monomer concentration. The catalysis of K2CO3was better than others, and the catalytic activity of K2CO3could be enhanced by dissolving it with amount of water, which can promote the formation of phenoxy salt, and the rate of the polymerization were faster.The ultrafiltration membranes were prepared by phase inversion process with PSF homopolymer or Bis-A/HQ/DCS copolymer, respectively. The flux and the rejection of ultrafiltration membrane was analyzed. The hydrophilic character of untrafiltration membranes was characterized by surface contact angle. The surface morphology and cross-sectional structure of ultrafiltration membranes were observed by Scanning Electron Microscope(SEM). And the mechanical strength of ultrafiltration membranes was also tested. The measurement showed that the hydrophilic Bis-A/HQ/DCS ultrafiltration membrane was more hydrophilic than PSF ultrafiltration membrane, and the separation performance of Bis-A/HQ/DCS ultrafiltration membrane was good. The SEM indicated that lots of micropores on the surface of ultrafiltration membrane, and the cross-sectional structure consists of a thin dense cortex layer and a loose spongy support layer.The Bis-A/HQ/DCS ultrafiltration membrane was applied to the recovery of dyes and fatliquoring materials from effluents of dyeing-fatliquoring process, and the effect of operating conditions on ultrafiltration was also discussed. The result of UF processes showed that the TSS, Chroma, TN, TDS and COD reduced100%,96.2%,86.6%,96.4%and91.8%, respectively. The flux recovery ratio of membranes reached96%after washing with cleaning solution (pH=10) The retentate stream can be reused in the dyeing-fatliquoring process and save about30%dyes and fatliquoring agent. The permeate stream that can be reused in the picking step before the tannage. The physical mechanical properties of leather treated with recoverd solutions was close to the leather which was made by the traditional technology. The UF process reduced the pollution of the leather industry to the environment, simplified the wastewater process, and saved chemicals and water.更多还原