PVDF ultrafiltration membranes of controlled performance via blending PVDF-g-PEGMA copolymer synthesized under different reaction times

PVDF blended different graft ratio of PVDF-g-PEGMA were systematically studied. Tuning the amphiphilic copolymer synthesis time to control membrane performance. The PVDF membrane with PVDF-g-PEGMA at 19 h possesses most surface oxygen content. The synthesis time of PVDF-g-PEGMA at 9 h is good for high flux UF membrane. Polyvinylidene fluoride grafted with poly(ethylene glycol) methyl ether methacrylate (PVDF-g-PEGMA) was synthesized using atomic transfer radical polymerization (ATRP) at different reaction times (9 h, 19 h, and 29 h). The corresponding conversion rates were 10%, 20% and 30%, respectively. PVDF was blended with the copolymer mixture containing PVDF-g-PEGMA, solvent and residual PEGMA under different reaction times. In this study, we explored the effect of the copolymer mixture additives with different synthesis times on cast membrane performance. Increasing the reaction time of PVDF-g-PEGMA causes more PVDF-g-PEGMA and less residual PEGMA to be found in the casting solution. Incremental PVDF-g-PEGMA can dramatically increase the viscosity of the casting solution. An overly high viscosity led to a delayed phase inversion, thus hindering PEGMA segments in PVDF-g-PEGMA from migrating to the membrane surface. However, more residual PEGMA contributed to helping more PEGMA segments migrate to the membrane surface. The pure water fluxes of the blended membrane with reaction times of 9 h, 19 h, and 29 h are 5445 L·m⁻²·h⁻¹, 1068 L·m⁻²·h⁻¹and 1179 L·m⁻²·h⁻¹, respectively, at 0.07 MPa. Delayed phase inversion can form smaller surface pore size distributions, thus decreasing the water flux for the membranes with PVDF-g-PEGMA at 19 h and 29 h. Therefore, we can control the membrane pore size distribution by decreasing the reaction time of PVDF-g-PEGMA to obtain a better flux performance. The membrane with PVDF-g-PEGMA at 19 h exhibits the best foulant rejection and cleaning recovery due to its narrow pore size distribution and high surface oxygen content.     

柠檬酸改性聚天冬氨酸阻垢剂的合成及性能研究

将柠檬酸、马来酸酐、氨共聚,在主链上引入羧基以改性聚天冬氨酸,提高了其阻垢性能。实验测定了不同反应条件下产品的阻垢性能,讨论了聚天冬氨酸共聚物的合成工艺条件。结果表明n(氨):n(MA):n(柠檬酸)=2.2:1:0.09,胺化时间2.5h,热聚温度170℃,热聚时间15min,合成的PASP共聚物用量为2mg/L时产品的阻垢效果最好。     

C60丙二酸二(2,4,6-三硝基苯乙基)酯马来酸聚合物铅盐的合成

以TNT和甲醛为原料,首先得到2,4,6-三硝基苯乙醇(TNPE),TNPE和丙二酰氯经酯化反应合成得到丙二酸二(2,4,6-三硝基苯乙基)酯(TNPEM),TNPEM与C60通过Bingel反应制备了C60丙二酸二(2,4,6-三硝基苯乙基)酯(FTNPEM).FTNPEM再与马来酸和硝酸铅通过共聚合成盐反应得到含能的C60丙二酸二(2,4,6-三硝基苯乙基)酯马来酸聚合物铅盐5.采用FT-IR、UV-Vis、GPC、XPS、XRD等表征方法对聚合物及其铅盐的结构进行了分析.利用差热分析法(DTA)和热重分析法(TGA)对聚合物铅盐5的热稳定性及其对RDX的热分解催化作用进行了研究.结果表明,在空气气氛下,聚合物铅盐5初始分解峰值温度为239℃,表明产物热稳定性良好.对RDX热分解催化作用研究结果表明,聚合物铅盐5能加速RDX的分解,并使RDX分解峰温降低6℃.     

混凝法处理丙烯腈-丁二烯-苯乙烯树脂废水

以聚合氯化铝铁为混凝剂、阴离子型聚丙烯酰胺为助凝剂,采用混凝法处理丙烯腈-丁二烯-苯乙烯树脂（ABS）废水（简称废水）,考察了聚合氯化铝铁加入量、沉降时间、搅拌转速、搅拌时间、废水pH和混凝温度对废水处理效果的影响。实验结果表明,在聚合氯化铝铁加入量50mg／L、阴离子型聚丙烯酰胺加入量2mg／L、废水pH6．0～8．0、快速搅拌1min、慢速搅拌6min、沉降时间25min、混凝温度20～25℃的条件下,废水的SS去除率达97％以上,COD去除率达77％以上。     

含聚乙烯氧基长侧链共聚物阻磷酸钙垢性能研究

以过硫酸铵为引发剂,含不同乙烯氧基重复单元数n的烯丙基聚乙烯氧基硫酸铵(ASn,n=5,10,15,20)和马来酸酐(MA)为单体在水溶液中聚合,合成对循环冷却水系统中磷酸钙垢有显著阻垢效果的共聚物MSn(n=5,10,15,20),并利用红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)对聚合物MS10结构进行了表征。采用静态阻垢方法探讨了共聚物MSn中n值以及聚合物用量、溶液中Fe2+、Ca2+、杀生剂和溶液pH值、溶液温度对共聚物阻磷酸钙垢性能的影响。结果表明MSn用量存在临界值效应,MS10阻磷酸钙垢性能最好,在投加量为6 mg/L时MS10阻磷酸钙垢率达92%,且在高Fe2+浓度、高Ca2+浓度、高pH值以及高温条件下具有优异的阻磷酸钙垢性能,与异噻唑啉酮杀生剂和含氯含溴杀生剂有很好的配伍性。实验表明MS10是一种性能优异的循环水用阻磷酸钙阻垢剂。     

混凝—气浮工艺预处理ABS树脂生产废水

采用混凝—气浮工艺对ABS树脂生产过程中的丁二烯聚合工段和乳液接枝工段混合废水进行预处理,优化了工艺条件。实验结果表明：最佳药剂组合为CaCl₂和阳离子型聚丙烯酰胺（FO4440SSH）,最佳CaCl₂投加量为75 mg/L,最佳FO4440SSH投加量为10 mg/L,最佳废水pH范围为5~7;最优操作条件为以288 r/min的转速搅拌混凝1 min,再以72 r/min的转速搅拌絮凝20 min;混凝阶段的最佳G值为159.9 s^-1、GT值为9 594,絮凝阶段的最佳G值为24.5 s^-1、GT值为29 400;优化条件下,废水的浊度与COD去除率均可达98%以上。     

Synthesis of lignin-based copolymer LSAA and the application on controlling non-point source pollution (NPS) resulted from surface runoff

In this article, alkali lignin separated from paper pulp waste was grafted into a novel copolymer LSAA (a copolymer of lignin, starch, acrylamide and acrylic acid). Its practical application effect and environmental safety were studied. The results of field simulation experiment indicated that the application of LSAA significantly affected the output of the runoff and pollutants. The runoff quantity was decreased by 16.67%-47.00% and the loads of total suspended solids (TSS), chemical oxygen demand (COD), total nitrogen (TN) and total phosphorus (TP) were reduced by 17.78%-62.14%, 26.32%-59.91%, 26.67%-42.86%, and 22.18%-52.78%, respectively. Tests on its environmental safety showed that LSAA did no harm the soil. Compared with polyacrylamide (PAM), a dominant product in this field, LSAA exhibited similar effects and cheap cost. Thus, this study not only created a new product for controlling runoff water quality but also offered a beneficial application for industrial paper waste.     

松香基三烯丙酯交联聚合树脂的合成及其对水中Pb（II）、Cd（II）和Cu（II）的吸附性能与机制

以自制的松香基三烯丙酯（triallyl maleopimarate， TAMP）为交联剂，通过悬浮聚合法合成了一种松香基三烯丙酯交联聚合树脂（triallyl maleopimarate-acrylic copolymer， TAMPA），采用红外光谱（FTIR）、扫描电镜（SEM）、N₂吸附脱附曲线和热重（TG）分析等方法对其物理化学结构及热稳定性等进行表征，采用批量吸附实验探讨了TAMPA投加量、溶液pH、温度、接触时间和离子强度等因素对TAMP树脂对Pb（II）、Cd（II）和Cu（II）重金属离子吸附性能的影响.结果表明，当pH值为2.0~5.0，TAMPA树脂对Pb（II）、Cu（II）和Cd（II）吸附量呈先增大后平缓的趋势，pH=5.0为最大值.随着离子溶液的增加对TAMP树脂去除重金属离子有抑制作用；吸附动力学符合准二级模型；Freundlich等温吸附模型可以较好地描述TAMPA对3种重金属的吸附；吸附热力学结果表明其能自发对相关金属离子进行吸附.以EDTA为洗脱剂，重复再生3次后TAMPA仍有可观的吸附性能.结合XPS和量子化学计算模拟结果，提出了TAMPA对Pb（II）、Cd（II）和Cu（II）的吸附作用机制，主要为重金属离子与材料基体中的C?O氧配位螯合作用.