高吸水树脂的等离子体引发聚合反应制备研究进展

介绍了等离子体引发聚合反应的特点;综述了等离子体引发聚合反应在制备高吸水树脂领域的研究进展,包括等离子体引发乙烯基系列单体聚合制备高吸水树脂、等离子体引发乙烯基系列单体接枝共聚制备高吸水树脂、等离子体引发制备有机-无机复合高吸水树脂等;最后指出了等离子体引发制备高吸水树脂研究需要加强的几个方向:即加强对等离子体引发聚合制备高吸水树脂反应机理的研究;加强天然产物接枝系列、有机-无机复合系列高吸水树脂以及多功能高吸水树脂的等离子体引发聚合制备研究等。     

"充填型"复合膜脱除水中微量有机氯化物的研究

利用等离子体照射引发接枝聚合方式制备了具有"充填型"结构的复合膜,在渗透汽化膜分离过程中研究了其从水中脱除微量有机氯化物的分离性能.该复合膜由两种材料组成;耐溶剂性能优良的高密度聚乙烯多孔基膜和接枝聚合后充填于基膜微孔中的聚丙烯酸甲酯,后者形成渗透汽化过程的分离选择性.使用FT-IR光谱图证实基膜接枝后表面存在羰基,表明形成接枝聚合的复合膜.在室温下进行渗透汽化实验,能够有效脱除水中微量的二氯甲烷、三氯甲烷和三氯乙烯,其中脱除二氯甲烷的渗透汽化分离因子超过2000,渗透通量达到120 g·(m2·h)- 1.     

粉末态高密聚乙烯的辐射接枝

引　言在过去 2 0年中 ,聚乙烯 (ＰＥ)的辐射接枝被广泛研究 ,主要集中在对聚乙烯膜或片体在溶液中的接枝研究 ,而有关聚乙烯粉末固相辐射接枝的研究却很少[1] .实际上 ,辐射接枝在高分子材料改性领域存在优势 ,尤其是在固态粉末体系中 ,辐射接枝比表面高、单体利用率高、均聚合可降至最低甚至消除、接枝产物在与聚合物共混时的相容性改善等[2 ] .通过辐射接枝可以制备选择性渗透膜、医用高分子材料和高分子吸着剂 ,此外还可引入极性基团增强聚合物的黏结力或附着力[1,3 ] .本文研究了粉末态高密聚乙烯的辐射效应、与多种单体的固态辐射接枝…     

预辐射接枝聚合制备新型质子交换膜

含氟聚合物薄膜因其优良的化学稳定性被广泛使用于离子交换膜领域,目前商品化程度最高的质子交换膜产品为全氟磺酸质子膜,但其合成工艺复杂且价格昂贵.以聚偏氟乙烯薄膜为基底,经高能电子束辐照活化薄膜,引发2-丙烯酰胺-2-甲基丙磺酸和甲基丙烯酸羟乙酯的自由基接枝聚合,一步制得质子交换膜.该合成过程以水和N,N'-二甲基甲酰胺作...     

温度感应式开关膜的接枝率对其开关特性的影响

利用等离子体诱导填孔接枝聚合法将聚(N-异丙基丙烯酰胺)（PNIPAM）接枝聚合在聚偏氟乙烯（PVDF）微孔膜上制备了一系列具有较宽接枝率范围的温度感应式开关膜,系统地研究了接枝率对膜的温度感应开关特性的影响.结果表明,开关膜的接枝率对膜的过滤通量、温度感应开关系数和膜孔径感温变化倍数都有十分重要的影响.接枝率在小于等于2.81%时,温度感应开关系数和膜孔径感温变化倍数均随接枝率增加而增加;而对于接枝率大于等于6.38%的膜,膜开关系数和膜孔径感温变化倍数总是趋近于1,膜不具备温度感应开关特性.为了获得预期的开关性能,必须将膜的接枝率控制在适当的范围.     

硅橡胶膜的改性与应用研究进展

对近年来硅橡胶膜通过复合、辐射接枝、过氧化物引发接枝和等离子体聚合改性．以及改性硅橡胶膜在有机废水处理、发酵、离子传感器和膜激活器等方面的研究与应用进行了概述。     

聚丙烯膜接枝改性亲和膜的制备与表征

采用预辐射接枝法在聚丙烯基膜(PP)上接枝甲基丙烯酸缩水甘油酯(GMA),再将配基辛巴蓝(CBD)固载于GMA聚合链上制备了一种亲和膜.考察了预辐射剂量、接枝单体浓度、反应时间和温度、Mohr's盐浓度对GMA聚合接枝的影响,获得了较佳的条件:GMA浓度20%(v/v),反应温度70℃,反应时间3h,Mohr's盐浓度0.01%(wt),CBD溶液浓度25mg·mL-1.用红外光谱 (FTIR)和扫描电镜 (SEM)分析和观察了该亲和膜的表面形貌特征;在37℃和60mg·L-1的胆红素溶液中对该亲和膜进行静态吸附平衡实验,结果表明,经2.5 h吸附达到平衡,其吸附容量可达50mg·g-1.     

反相乳液法mSt-g-AM接枝共聚反应的动力学模型

采用反相乳液法进行淀粉与丙烯酰胺接枝共聚反应的机理研究,考察以过硫酸铵引发机械活化淀粉(mSt)与丙烯酰胺(AM)接枝共聚反应速率Rg与引发剂浓度[I]、乳化剂浓度[E]、单体浓度[M]和淀粉浓度[mSt]的关系,推导并验证该反应体系的动力学模型及反应机理。结果表明,本实验得出的动力学关系式为:[][][][]1.24 0.76 1.54 0.33gR∞mSt I M E,与理论推导出的动力学关系式:[][][][]0.5~1 0.5~1 1~1.5 0.6pR∞mSt I M E基本一致,机械活化淀粉与丙烯酰胺在反相乳液中进行接枝共聚反应符合自由基聚合机理;在聚合过程中,引发剂分解副反应、诱导分解及"笼壁效应"导致引发效率降低,单基终止和双基终止反应同时存在;推导出共聚物消耗单体量与参加反应单体总量的比值(X):[][][][][][][]0.5 0.50.5 0.5 0.5 0.51 2 31/X=1+KM/mSt+KmSt I/M+KI/mSt,单体浓度、淀粉乳浓度和引发剂浓度对其有重要影响。     

功能化聚烯烃接枝共聚物的制备和应用研究新进展

介绍了制备功能化聚烯烃接枝共聚物的意义及近年来功能化聚烯烃接枝共聚物的设计与合成中的应用研究新进展,重点评述了制备功能化聚烯烃接枝共聚物时所采用的3种方法,I偶合接枝法;II引发接枝法:1阴离子聚合;2硼氧自由基存在下的控制自由基聚合;3原子转移自由基聚合(ATRP);4氮氧自由基存在下的控制自由基聚合(NMRP);5可逆加成-裂解链转移活性自由基聚合(RAFT);III直接接枝法,并对上述方法进行了简单的优缺点对比。随后介绍了功能化聚烯烃接枝共聚物的应用。最后对功能化聚烯烃接枝共聚物的未来发展趋势进行了展望,认为对新型、高效、实用的制备方法的探索以及实际应用将是功能化聚烯烃接枝共聚物领域的主要研究方向。     

界面聚合表面改性法制备高效抗污染油水分离复合膜

引　言油污染作为一种常见的污染 ,对环境保护和生态平衡危害极大 .膜分离法则是对含油污水进行深度处理的可行而有效的方法[1] .在使用膜分离法理含油污水时 ,膜污染是影响分离过程的最主要问题 .提高膜表面的亲水性能有效缓解膜分离含油污水过程中的膜污染情况[2 ,3] .目前处     

Synthesis of monodisperse nonporous crosslinked poly(glycidyl methacrylate) particles with metal affinity ligands for protein adsorption

Monodisperse nonporous crosslinked poly(glycidyl methacrylate) (PGMA) particles with immobilized metal affinity ligands were prepared for selective recovery of proteins. The PGMA particles, with an average size of 2.2 µm, were prepared by a simple dispersion polymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA). The particles were characterized by scanning electron microscopy (SEM) and Fourier‐transform infrared spectroscopy (FTIR). The epoxy groups of the particles were modified with the metal chelating agent iminodiacetic acid (IDA), which forms metal–IDA chelates at the active sites. After charging with copper ions, the particles were used to recover a model protein, bovine hemoglobin (BHb), in a batchwise manner. The particles had the adsorption capacity of 218.7 mg g⁻¹ with little nonspecific adsorption. The adsorption behavior could be described with the Langmuir equation. The effect of pH on the adsorption was also studied. Regeneration of the metal‐chelated particles was easily performed with 50 mmol L⁻¹ ethylenediaminetetraacetic acid (EDTA), followed by washing with water and reloading with Cu²⁺. The particles could be very useful as an affinity separation adsorbent. Copyright © 2005 Society of Chemical Industry     

Adsorption and desorption properties of the chelating membranes prepared from the PE films

The chelating membranes for adsorption of metal ions were prepared by the photografting of glycidyl methacrylate (GMA) onto a polyethylene (PE) film and the subsequent modification of the resultant GMA‐grafted PE (PE‐g‐PGMA) films with disodium iminodiacetate in an aqueous solution of 55% DMSO at 80°C. The adsorption and desorption properties of the iminodiacetate (IDA) group‐appended PE‐g‐PGMA (IDA‐(PE‐g‐PGMA)) films to Cu²⁺ ions were investigated as functions of the grafted amount, pH value, Cu²⁺ ion concentration, and temperature. The amount of adsorbed Cu²⁺ ions increased with an increase in the pH value in the range of 1.0–5.0. The time required to reach the equilibrium adsorption decreased with an increase in the temperature, although the degree of adsorption stayed almost constant. The amount of Cu²⁺ ions desorbed from the (IDA‐(PE‐g‐PGMA)) films increased and the time required to reach the equilibrium desorption decreased with an increase in the HCl concentration. About 100% of Cu²⁺ ions were desorbed in the aqueous HCl solutions of more than 0.5M. The amounts of adsorbed and desorbed Cu²⁺ ions were almost the same in each cyclic process of adsorption in a CuCl₂ buffer at pH 5.0 and desorption in an aqueous 1.0M HCl solution. These results indicate that the IDA‐(PE‐g‐PGMA) films can be applied to a repeatedly generative chelating membrane for adsorption and desorption of metal ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99:1895–1902, 2006     

Highly selective adsorption of Pt(IV) from spent catalyst by polyethyleneimine functionalized polyethylene/polypropylene non-woven fabric

Aiming at efficient recovery of platinum (Pt) from aqueous solution, the aminated polyethylene/polypropylene non-woven fabric (PE/PP NWF) was synthesized via radiation grafting of glycidyl methacrylate (GMA), followed by ring-opening reaction with polyethyleneimine (PEI). The effects of different parameters, including pH, sorption time, initial Pt(IV) concentration, competing ions and adsorbent dosage on the Pt(IV) adsorption performance were investigated by batch adsorption tests. A high Pt(IV) adsorption capacity of 485.0 mg g⁻¹ (initial concentration: 263.5 mg L⁻¹) was achieved, and the adsorption kinetics and isotherm conformed to the pseudo-second-order model and the Langmuir isotherm model, respectively. Moreover, the PEI functionalized PE/PP NWF exhibited excellent adsorption performance over the wide pH range (1–6), and also good selectivity for Pt(IV) over multiple coexisting metal cations (Ni, Cu, Co, Pb, Mg, and Zn). The recovery ratio of Pt from spent proton exchange membrane fuel cell (PEMFC) catalysts reached 89.7% after three cycles of regeneration.     

HDPE chelate membranes prepared by preirradiation grafting for adsorption of heavy metal ions

A new chelate membrane was prepared by grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene membranes and subsequent amination of poly‐GMA graft chains. The effects of grafting conditions such as radiation dose and temperature on grafting yield were studied. Effects of various parameters such as grafting yield, pH, and adsorption time on the metal uptake were investigated. The results show that the maximum metal uptake followed as given in the order Cr (III)>Fe (III)>Cu (II)>Cd (II). The metal uptake increased with grafting yield, adsorption time, pH of the medium, and initial concentration. The chelated metal ions are easily desorbed with 0.1 mol/L hydrochloric acid at room temperature. The results obtained from the chelate membrane showed a promising application in extraction of heavy metal ions from industrial effluents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Free radical grafting of itaconic acid and glycidyl methacrylate onto PP initiated by organic peroxides

Comparative analysis was conducted to learn the grafting of itaconic acid (IA) and glycidyl methacrylate (GMA) onto polypropylene (PP) in the course of reactive extrusion. Seven organic peroxides, which satisfactorily dissolve in PP, but do not dissolve in the monomer, were used to initiate free‐radical reactions. The grafting of IA and GMA onto PP initiated by certain peroxides gave approximately equal amounts of grafted product. It was learned that the nature of peroxide initiators is decisive for grafting efficiency and degree of macromolecular degradation. To ensure a high yield of grafted product, it is advisable to use peroxides, which have thermodynamic affinity with PP and the temperature range of decomposition of which corresponds to the thermal regime of reactive extrusion. Di(tert‐butyl peroxy‐isopropyl)‐benzene (P‐14) appeared to meet for the most these requirements for grafting both GMA and IA. Grafting is accompanied by β‐decomposition of the chains irrespective of the type of peroxide and monomer used; hence, the MFI increases. A considerable rise in MFI was observed at a minimum peroxide concentration (0.1wt %). Degradation of PP during modification eases its crystallization from the melt. In this case the crystallization temperature is 5 to 8.5°C higher than of the original PP, and the crystallinity degree increases by 20 to 60%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 64–72, 2002     

Nondegradative melt functionalization of polypropylene with glycidyl methacrylate

The melt grafting of glycidyl methacrylate (GMA) onto powdered isotactic polypropylene (PP) in a Haake Rheocord RC90 mixer was studied. Grafting degrees were determined by nonaqueous back titration of trichloroacetic acid with sodium hydroxide. The extent of degradation and crosslinking of PP during grafting was indicated by the melt-flow rates (MFR) of the grafted samples. The influences of GMA concentration, initiator type and concentration on grafting degree, reaction efficiency, and degradation were evaluated. A novel method was developed to obtain a high grafting degree with little degradation of PP using acrylamide (AM) as the initiating agent. The grafting process occurred before or during the melting of PP (i.e., solid-state grafting), at which temperature crosslinking is preferred over chain scission. Primary free radicals generated from the rapid decomposition of AM have a higher tendency to attack GMA molecules than PP chains. At the same estimated amount of primary radicals, both grafting degree and grafting efficiency increase with decreasing decomposition temperature of the initiator (for the same decomposition half-life) in the order of AM > benzoyl peroxide (BPO) > 2,5-di(t-butylperoxy)-2,5-dimethyl-3-hexyne (LPO). FunctionalizedPP with the desired grafting degree and little degradation of PP could be obtained by the use of mixed initiators. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1957–1963, 1998     

Polyethylenimine‐grafted and HSA‐immobilized poly(GMA–MMA) affinity adsorbents for bilirubin removal

The epoxy‐group‐containing microspheres from cross‐linked glycidyl methacrylate and methyl methacrylate, poly(GMA–MMA), were prepared by suspension polymerisation. The epoxy groups of the poly(GMA–MMA) microspheres were used for grafting with an anionic polymer polyethylenimine (PEI) to prepare non‐specific affinity adsorbents (poly(GMA–MMA)–PEI) for bilirubin removal. The specificity of the poly(GMA–MMA)–PEI adsorbent to bilirubin was further increased by immobilization of human serum albumin (HSA) via adsorption onto PEI‐grafted poly(GMA–MMA) adsorbent. Various amounts of HSA were immobilized on the poly(GMA–MMA)–PEI adsorbent by changing the medium pH and initial HSA concentration. The maximum HSA content was obtained at 68.3 mg g^?1 microspheres. The effects of pH, ionic strength, temperature and initial bilirubin concentration on the adsorption capacity of both adsorbents were investigated in a batch system. Separation of bilirubin from human serum was also investigated in a continuous‐flow system. The bilirubin adsorption on the poly(GMA–MMA)–PEI and poly(GMA–MMA)–PEI–HSA was not well described by the Langmuir model, but obeyed the Freundlich isotherm model. The poly(GMA–MMA)–PEI affinity microspheres are stable when subjected to sanitization with sodium hydroxide after repeated adsorption–desorption cycles. Copyright © 2004 Society of Chemical Industry     

Surface modification of nylon membrane by glycidyl methacrylate graft copolymerization for antibody immobilization

Surface of nylon membrane was modified by the graft copolymerization of glycidyl methacrylate (GMA) using persulfate and thiosulfate as redox initiator system. Effect of various reaction parameters such as initiator concentration, monomer concentration, polymerization time, and temperature on degree of grafting was also studied. Maximum grafting of 100% was achieved by using equimolar concentration (0.008M) of redox initiator and 0.5M of GMA monomer at 70°C in 60 min. Grafted nylon membranes with various graft levels of GMA were characterized by various techniques such as fourier transform infrared spectroscopy, thermo gravimetric analysis, and scanning electron microscopy. The GMA grafted nylon (NyM‐g‐GMA) membranes with different graft levels were evaluated as a support for immobilization of rabbit anti goat antibody (RAG IgG). Antibody (Ab) immobilized NyM‐g‐GMA membranes were evaluated using ELISA and Bradford protein estimation method. Nylon membrane with 60% graft level showed optimum immobilization of Ab at RAG IgG conc. of 0.625 μg/mL with low nonspecific binding. Maximum immobilization efficiency (I.E.%) of 56% was observed for membrane with 60% graft level at 50 μg/mL of RAG IgG in PBS (pH 7.4). Ab immobilized NyM‐g‐GMA discs were found to be stable up to 6 weeks at 4°C and 2 days at 37°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adsorption of Pb2+, Cu2+ and Co2+ by polypropylene fabric and polyethylene hollow fiber modified by radiation-induced graft copolymerization

Cation-exchange adsorbents were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) fabric and polyethylene (PE) hollow fiber and subsequent phosphonation of epoxy groups of poly(GMA) graft chains. The adsorption characteristics of Pb²⁺, Cu²⁺ and Co²⁺ for the two cation-exchange adsorbents were studied. In the grafting of GMA onto PP fabric, the degree of grafting (%) increased with an increase in reaction time, reaction temperature, and pre-irradiation dose. The maximum grafting yield was observed around 60% GMA concentration. In 50, 130 and 250% GMA-grafted PP fabric, the content of phosphoric acid was 1.52, 3.40 and 4.50 mmol/g at 80 °C in the 85 % phosphoric acid aqueous solution for 24 h, respectively. The adsorption of Pb²⁺, Cu²⁺ and Co²⁺ by PP fabric adsorbent was enhanced with an increased phosphoric acid content The order of adsorption capacity of the PP fabric adsorbent was Pb²⁺>Co²⁺>Cu²⁺. In adsorption of Pb²⁺, Cu²⁺ and Co²⁺ by PE hollow fiber, the amount of Pb²⁺ adsorbed by the PE hollow fiber adsorbent containing 1.21 mmol/g of -PO₃H wasca. 54.4 g per kg. The adsorption amount of Cu²⁺ and Co²⁺ in the same PE hollow fiber wasca. 21.0 g per kg andca. 32.1 g per kg, respectively. The order of adsorption of the PE hollow fiber adsorbent was Pb²⁺>Co²⁺>Cu²⁺.     

Papain Adsorption on Chitosan-Coated Nylon-Based Immobilized Metal Ion (Cu2+, Ni2+, Zn2+, Co2+) Affinity Membranes

A novel immobilized metal affinity membrane was prepared for papain adsorption in this article. Higher papain adsorption capacity between 43-67 mg/g was observed and the adsorption isotherm fitted the Freundlich equation. Experimental data were analyzed using two adsorption kinetic models. The pseudo-second-order kinetic model provided better correlation to the experimental results. A significant amount of the adsorbed papain was eluted by 1.0 M NaSCN at pH 5.0 for all affinity membranes. It was concluded that the novel chitosan-coated nylon-based immobilized metal ion affinity membrane could be applied for the large-scale isolation of papain without resulting in enzyme denaturation.