Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Styrene-PEG (600) DMA Crosslinked Polymers for Absorption of Oil Derivatives

In this work, styrene (St) based crosslinked polymers were prepared for removal of oil derivatives from aqueous solutions. Polyethylene glycol (600) dimethacrylate (PEG (600) DMA) was used as crosslinker in synthesis of styrene based crosslinked polymers, for the first time. The polymers were characterized by FTIR, SEM, elemental analysis and solvent (toluene, chloroform and fuel-oil) absorption capacities. The effects of different reaction parameters like crosslinker type, diluents amount and the presence of pore forming agent on the absorption properties of polymers were investigated. The polymers synthesized by using PEG (600) DMA have higher solvent absorption capacity than that of synthesized by using conventional crosslinker. Furthermore, the polymers synthesized in the presence of good diluents have higher absorption capacities. The addition of pore forming agent into the reaction medium has also improved the absorption rate of polymers. The absorption capacity of polymers in different solvents is in order of chloroform > toluene > fuel-oil. It was seen that oil derivatives can be removed efficiently from water by the St-PEG (600) DMA polymers.     

Preparation and properties of two-component hydrogels based on 2-acrylamido-2-methylpropane sulphonic acid

Xerogels comprising 2-acrylamido-2-methylpropane sulphonic acid (AMPS) and acrylic acid as well as AMPS and acrylamide crosslinked with hexafunctional crosslinking agent have been prepared by catalytic initiation polymerization to complete conversion. Different percentages of hexafunctional crosslinker, 1,1,1-trimethylolpropane trimethacrylate, were used to prepare crosslinked copolymers having different degree of crosslink densities. The crosslinked copolymers were swollen in water to equilibrium. The volume fraction of polymer, the swelling capacity and the equilibrium water content were obtained. Low conversion polymerization was used to determine the reactivity ratios of both monomer pairs. Fourier transform spectroscopy was utilized to measure the molar ratio of copolymers constituents. © 1998 John Wiley & Sons, Ltd.     

Inverse Suspension Polymerization of Partially Neutralized and Lightly Cross-Linked Acrylic Acid: Effect of Reaction Parameters

An inverse suspension polymerization was carried out in laboratory in one Liter Buchi glass reactor to produce superabsorbent polymers (SAPs) based on acrylic monomers for hygiene applications. Strongly water absorbing polymers, based on acrylic acid, sodium acrylate were prepared by copolymerization using potassium per sulfate as initiator and N-N′ methylene-bisacrylamide (MBA) as crosslinking agent. The effect of varying monomer, crosslinker, initiator, dispersant concentration, time of reaction and degree of neutralization, on absorption capacities was investigated. In the present studies, the continuous hydrocarbon phase was taken as 50:50 mixture of n-heptane and cyclohexane (aliphatic-alicyclic) because the availability of crosslinker in the aqueous phase is controlled by the partition coefficient of the crosslinker between the aqueous phase and the continuous hydrocarbon phase. The SAPs were evaluated for their free absorption capacities in distilled water, saline (0.9% NaCl), and also absorption under load (AUL). The experimental results show that these SAPs have good absorbency both in water and NaCl solutions. It was observed that SAP synthesized from acrylic acid with about 70% degree of neutralization, containing 1% cross-linker, and 0.5–1.0% initiator concentration with 10% dispersant exhibited absorption capacities in water, saline and AUL as 220 g/g, 70 g/g and 27 g/g respectively.     

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composite: Preparation,swelling investigation and its application as a slow-release fertilizer

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composites (SACs) were prepared by graft copolymerization of acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) onto sodium alginate (Na-Alg) in the presence of montmorillonite (MMT) using N,N′-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (KPS) as an initiator in aqueous solution. The composite structures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscope (SEM). The effect of % initiator, crosslinker amount and clay ratio on the swelling capacity was investigated. The results indicated that the highest swelling capacity of the composites in distilled water was 752 g/g by using 1.25% KPS and 0.06% MBA, 75% AA, 6.25% HEMA and 12.5% Na-Alg. Different samples were loaded with urea to evaluate their release potentials, and the release was studied by measuring the conductivity. The amount of urea release increased with increasing MMT amount.     

Synthesis,characterization, and evaluation of polymeric oil sorbent for remediation of hydrocarbons spillage

The preparation and evaluation of polymeric oil sorbent based on styrene acrylate ester and ethylhexyl acrylate (EHA) are the main target of this work. In this respect, poly styrene-co-p-chloromethyl styrene (PSCMS) was synthesized through radical copolymerization of p-CMS with styrene in the presence of benzoyl peroxide initiator. Then, the PSCMS was reacted with acrylic acid to produce macromonomer containing polymerizable C?C poly {styrene-co-[4-(methyl acrylate) styrene]} (PSSMA) that subsequently copolymerized with EHA in the presence of a cross-linker to obtain the cross-linked copolymers PSSMA/EHA (organogel). The prepared compounds were characterized by using FTIR, ¹H NMR, and gel permeation chromatography. The thermal properties of the cross-linked oil absorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The oil absorbency of oil gel was determined through oil absorption tests; the highest oil absorbencies of oil gel were found to be 82.6, 74.4, 46.7, and 38.1 g/g in N,N-dimethyl formamide, CHCl₃, toluene, and diesel, respectively.     

Preparation and characterization of poly(acrylic acid)‐iron rich smectite superabsorbent composites

A novel poly(acrylic acid)‐iron rich smectite (IRS) superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) in the presence of N,N‐methylenebisacrylamide (MBA) as a crosslinker. IRS was used to strengthen the hydrogel products in the polymerization process. Water absorbencies for these superabsorbent composites in water and saline solutions were investigated. IRS caused a reduced equilibrium swelling as low as 8–26%. However, grafted IRS particles resulted in improved gel strength as high as 66% compared to the IRS‐free sample. IRS modified superabsorbent hydrogel composites exhibited higher thermal stability compared to the IRS‐free sample. The pH dependent reversible swelling behavior of hydrogels was also investigated. It is found that the swelling process is pH dependent and reversible for synthesized superabsorbent. Superabsorbent hydrogel composites were characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR spectroscopy was confirmed grafting of acrylic chains onto the surface of IRS particles. From the standpoint of these results, these strengthened and thermostabilized hydrogels may be considered as good candidates for a controlled release study and agricultural applications. Copyright © 2007 John Wiley & Sons, Ltd.     

新型两性聚电解质高吸水性树脂CMCTS-g-（PAA-co-PTMAAC）的制备研究

通过氧化还原引发荆引发的接枝共聚反应,使阴离子型单体丙烯酸(AA)和阳离子型单体三甲基烯丙基氯化铵(TMAAC)在羧甲基壳聚糖(CMCTS)的分子链上接枝共聚,制得羧甲基壳聚糖接枝-(聚丙烯酸-co-聚三甲基烯丙基氯化铵)(CMCTS-g-(PAA-co-PTMAAC)两性聚电解质高吸水性树脂.采用红外光谱对产物的结构进行了表征,比较了反应条件对产物吸液性能的影响.发现制备具有良好吸液性能的高吸水性树脂的最优化反应条件为:TMAAC占单体总质量的14.3%,mNNMBA/mAA值在0.014附近,单体总质量为CMCTS质量的9.33倍,丙烯酸中和度在20%～30%之间.研究发现,随外部溶液pH值的变化,两性聚电解质高吸水性树脂的溶胀性能在酸性和碱性条件下各有一个最大值,在等电点处产物的吸液性相对较低.     

多孔壳聚糖接枝聚丙烯酸/钠基蒙脱土复合高吸水凝胶的制备及其对Pb2+的吸附

以十二烷基苯磺酸钠(SDS)胶束为孔模板,过硫酸铵(APS)引发,N,N'-亚甲基双丙烯酰胺(MBA)交联,壳聚糖(CS)与丙烯酸(AA)、钠基蒙脱土(Na-MMT)在水溶液中接枝共聚,成功制备了多孔壳聚糖接枝聚丙烯酸/钠基蒙脱土(CS-g-PAA/Na-MMT)复合高吸水凝胶,提出了SDS胶束致孔机理。扫描电子显微镜(SEM)分析表明,添加SDS的样品,凝胶表面出现多孔结构。通过考察SDS浓度对复合高吸水凝胶平衡吸水倍率和吸水速率的影响,发现当SDS浓度为1.5 mmol/L时,复合凝胶在蒸馏水和生理盐水中的平衡吸水倍率相对于空白样分别提高53.9%和35.3%,初始溶胀速率常数K_is也由空白样的1.2652 g/(g·s) 提高到5.1680 g/(g·s)。多孔结构也使复合凝胶对Pb²⁺的吸附速率加快,在10 min内即可达到饱和吸附量的95%,30 min完全达到吸附平衡。     

Optimized synthesis and characterization of polystyrene graft copolymers and preliminary assessment of their biodegradability and application in water pollution alleviation technologies

With more and more plastics being employed in human lives and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. Keeping in view the environmental pollution caused by the waste polystyrene and to make the waste polystyrene technologically important, we have modified/functionalized the polystyrene with natural polymers and hydrophilic monomer through graft copolymerization. The present paper discusses the optimum conditions for the synthesis of graft copolymers and characterization of these polymers with SEMs and FTIR and thereafter biodegradation studies of these polymers by soil burial method. The present paper also discusses the effect of crosslinker concentration on the swelling and metal ion sorption (As⁺⁵ uptake) through the functionalized polystyrene, with the intention to make use of these polymeric networks in water pollution alleviation technology. It has been observed that percent As⁵⁺ uptake decreases from 80% to 60% as the crosslinker concentration increases from 0.032 mM to 0.162 mM in the polymeric networks. It has also been observed from the degradation studies that the grafting of starch onto polystyrene has induced 37% degradation after 160 days soil burial treatment and no degradation has been observed in case of grafting of acrylic acid onto polystyrene.     

Properties of polyurethane-polystyrene graft copolymer membranes used for separating water-ethanol mixtures

Polyurethane prepolymers (PU) based on hydrophilic poly(ethylene glycol) (PEG), hydroxypropyl acrylic acid (HPA), 2,4-toluene diisocyanate (TDI), and butanediol (BDO) were prepared by one-step polymerization with butanediol as the chain extender. Polyurethane-polystyrene graft copolymers (PU-g-PS) were synthesized by free radical copolymerization of PU with styrene (ST), 2,2′-azobisisobutyronitrile (AIBN) was used as initiator and toluene as solvent. Experimental results showed that the crosslinked membranes of PU-PS graft copolymers could be used for separating ethanol-water mixtures. The highest value of the separation factor (α) of the crosslinked separation membranes can reach 17.3. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were used to characterize the properties of PU-PS crosslinked membranes.     

Preparation and properties of some water-soluble,comb-shaped,amphiphilic polymers

Water-soluble comb-shaped polymers were prepared through grafting of poly(ethylene glycol) monomethyl ethers (MPEG) onto acrylic and methacrylic ester copolymers by transesterification reactions. The grafting was alkali-catalyzed, and performed in refluxing toluene solution or in melt at 155°C. The grafting efficiency was found to be on the order of 1 graft/10 monomer units. Epoxy groups in glycidyl methacrylate copolymers were also utilized for grafting. The crude graft copolymers were purified through chromatography and characterized by NMR and IR spectroscopy. Polymers prepared from MPEG 2000 were crystalline with melting points 10–15°C lower than the MPEG used. All polymers were shown to be surface active with CMC on the order of 1.5 g/L, and surface tensions of 38–45 dyn/cm. When used as emulsifiers the graft copolymers containing bulky lipophilic ester groups (2-ethylhexyl t-butyl) gave oil-in-water (o/w) and water-in-oil (w/o) emulsions from xylene/water with higher stability than those containing straight chain ester groups (methyl nbutyl n-docecyl). The most stable emulsions were obtained by dissolving the polymers in the organic phase.     

一步法合成大孔丙烯酸交联树脂

悬浮聚合;二乙烯苯;一步法合成大孔丙烯酸交联树脂     

Modified carrageenan 3. Synthesis of a novel polysaccharide-based superabsorbent hydrogel via graft copolymerization of acrylic acid onto kappa-carrageenan in air

A novel biopolymer-based superabsorbent hydrogel was synthesized through chemically crosslinking graft copolymerization of acrylic acid (AA) onto kappa-carrageenan (κC), in the presence of a crosslinking agent and a free radical initiator. A proposed mechanism for κC-g-polyacrylic acid was suggested and the affecting variables onto graft polymerization (i.e. the crosslinker, the monomer and the initiator concentration, the neutralization percent and reaction temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Maximum water absorbency of the optimized final product was found to be 789 g/g. The swelling capacity of the synthesized hydrogels was also measured in various salt solutions. The time-temperature profile of the polymerization reaction, in order to investigate the effect of molecular oxygen was conducted in terms of the absence and presence of the atmospheric oxygen. The overall activation energy (E_a) of the graft polymerization reaction was found to be 2.93 KJ/mol.     

New composite membranes based on crosslinked poly(acrylic acid) and porous polyethylene films

A process for the preparation of new composite membranes via free-radical copolymerization of acrylic acid with a macromolecular crosslinker (allyloxyethylcellulose) on the surface of porous polyethylene films was proposed. To reveal the effect of the porous matrix on the properties of the composites, homogeneous hydrogel membranes based on crosslinked poly(acrylic acid) were studied. The swelling ratio and transport characteristics of the membranes during separation of ethanol-water mixture by pervaporation were determined depending on the ethanol concentration. It was found that all membranes at low ethanol concentrations (0–30 vol %) exhibited high swelling ratios, which drastically decreased in the range 30–40 vol % as a result of gel collapse. The composite membranes had a higher selectivity for water over a broad range of ethanol concentrations than homogeneous membranes, but a lower flux. It was found that the strength and elasticity of porous matrices was retained in the composite membranes, which became mechanically more isotropic owing to the presence of the crosslinked component.     

Modified chitosan 4. Superabsorbent hydrogels from poly(acrylic acid-co-acrylamide) grafted chitosan with salt- and pH-responsiveness properties

Graft copolymerization of mixtures of acrylic acid (AA) and acrylamide (AAm) onto chitosan was carried out by using potassium persulfate (KPS) as a free radical initiator in the presence of methylenebisacrylamide (MBA) as a crosslinker. The effect of reaction variables, such as MBA concentration and AA/AAm ratio on the water absorbency capacity have been investigated. The polymer structures were confirmed by FTIR spectroscopy. Water absorbencies were compared for the hydrogels before and after alkaline hydrolysis. In the non-hydrolyzed hydrogel, enhanced water absorbency was obtained with increasing AA in monomer feed. However, after saponification, the sample with high AAm ratio exhibited more water absorbency. These behaviors were discussed according to structural parameters. The swelling kinetics of the superabsorbing hydrogels was studied as well. The hydrogels exhibited ampholytic and reversible pH-responsiveness characteristics. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The hydrogels exhibited salt-sensitivity and cation exchange properties. The pH-reversibility and on-off switching properties of the hydrogels make the intelligent polymers as good candidates for considering as potential carriers for bioactive agents, e.g. drugs.     

Superabsorbent materials derived from hydroxyethyl cellulose and bentonite: Preparation,characterization and swelling capacities

Superabsorbent polymers (SAPs) and composites (SAPCs) were prepared entirely by graft copolymerization of polyacrylamide (PAM) onto hydroxyethyl cellulose (HEC), using potassium persulfate (KPS) as an initiator, and N,N′-methylenebisacrylamide (MBA) as a crosslinker, in an aqueous solution. The extent of grafting was evaluated from % grafting efficiency (%GE) for various HEC/AM ratios, and a near optimal ratio was determined. Influences of various preparation parameters, i.e., the ratio of HEC/AM, amount of initiator and crosslinker, reaction temperature and time, and amount of filler on water swelling capacity of SAPs and SAPCs were studied. An FT-IR determination confirmed that the PAM was successfully grafted onto the HEC backbone, by showing absorption bands of the HEC backbone and new absorption bands from the grafted copolymer. The swelling capacity of SAPs and SAPCs depended strongly on different parameters, and the maximum swelling capacity was over 426 g/g and 538 g/g for the SAPs and SAPCs, respectively.     

丙烯酸交联壳聚糖渗透汽化膜研究（Ⅰ）——膜结构及交联机理

报道了一种新型渗透汽化膜－－丙烯酸交联壳聚糖膜，通过溶胀、拉伸、渗透汽化分离以及红外光谱等手段研究了膜的结构和交联机理。实验结果表明，交联反应由两部分组成：丙烯酸的双键和壳聚糖的氨基的加成反应和丙烯酸另一端的羧基和壳聚糖的氨基的酸碱中和反应。     

Swelling Behavior of pH-Sensitive Copolymers Containing 2-Acrylamido-2-Methyl Propane Sulfonic Acid and Acrylic Acid Crosslinked with Vinyl Trimethoxy Silane Crosslinker

Copolymers of 2-acrylamido-2-methyl propane sulfonic acid and acrylic acid were crosslinked in the presence of different mol% of either vinyl trimethoxy silane (VTMS) as the crosslinking agent under acidic conditions or N,N-methylenebisacrylamide (MBA) as crosslinker using solution radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Soluble fractions of the crosslinked networks were reduced by varying the MBA and VTMS concentrations. The surface morphology of the crosslinked polymers was observed by scanning electron microscope. The influence of pH on the swelling behavior of gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity.     

PAAM高吸水树脂反相悬浮聚合

采用反相悬浮聚合法,通过部分中和丙烯酸与丙烯酰胺共聚制备了聚(丙烯酸-丙烯酰胺)(PAAM)高吸水树脂,讨论了聚合过程主要影响因素对其吸液性能的影响,并对其进行了FTIR、TGA测试,得到最佳的合成工艺配方:单体质量浓度为30%,中和度N为75%,丙烯酸与丙烯酰胺的摩尔比为7∶3,交联剂、引发剂和分散剂质量浓度分别为0.065%、0.7%和0.5%(相对于单体总质量),单体溶液的滴加速度为2～3mL/min,聚合温度和时间分别为70℃和1.5h。此时在蒸馏水、0.9%NaCl溶液%(wt)中最大吸水倍率分别为Qw=1300g/g、Qs=93g/g(Qw为蒸馏水中吸水倍率,Qs为0.9%NaCl溶液中的吸水倍率,下同),树脂在320℃之前都是比较稳定的,可以适应较高的使用温度。