Preparation and characterization of acrylic acid‐treated bacterial cellulose cation‐exchange membrane

The feasibility of using bacterial cellulose as a source for environmentally compatible ion‐exchange membranes (IEM) was studied. Bacterial cellulose was modified with cation‐exchangeable acrylic acid (AAc) by UV‐graft polymerization to prepare membranes having ion‐exchange capacity (IEC) and greater structural density. Fourier transform infrared (FTIR) spectra showed that acrylic acids were successfully bound to bacterial cellulose. Morphological changes of acrylic acid‐treated bacterial cellulose were examined through scanning electron microscopy. A dense structure of the membrane increased with increasing UV‐irradiation time. Acrylic‐modified bacterial cellulose membrane showed reasonable mechanical properties, such as tensile strength of 12 MPa and elongation of 6.0%. Also the prepared membranes were comparable to the commercial membrane CMX in terms of the electrochemical properties, ie IEC of 2.5 meq g^?1‐dry mem, membrane electric resistance of 3 ohm cm², and transport number of 0.89. Copyright © 2003 Society of Chemical Industry     

球形木素基正离子交换树脂的制备与性能

以木素磺酸钙为原料,在一种价廉无毒的分散介质中通过反相悬浮聚合制备了球形木素基正离子交换树脂。研究了分散介质和分散剂用量、聚合温度及搅拌速度等多种因素对聚合反应和成球效果的影响,并对交换树脂的形貌、粒径、含水量、密度、交换容量及吸附性能进行表征与测;定。结果表明,在实验室条件下,交换树脂对;Cr^3＋的饱和吸附量达到59．28mg／g（干树脂）。     

Poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium): Synthesis,characterization, and its potential application for the removal of metal ions from aqueous solution

In the current study, poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium), poly(VP‐co‐AMPS), was prepared and used for the removal of Cu²⁺, Cd²⁺, and Ni²⁺ ions via a polymer‐enhanced ultrafiltration (PEUF) technique. The copolymer was synthesized by radical polymerization in an aqueous medium with a comonomer feed composition of 50:50 mol %. The molecular structure of the copolymer was elucidated by ATR‐FTIR and ¹H NMR spectroscopy, and the average molecular weight was obtained by GPC. The copolymer composition was determined to be 0.42 for VP and 0.58 for AMPS by ¹H NMR spectroscopy. The copolymer and homopolymers exhibited different retention properties for the metal ions. PAMPS exhibited a high retention capacity for all of the metal ions at both pH values studied. PVP exhibited selectivity for nickel ions. Poly(VP‐co‐AMPS) exhibited a lower retention capacity compared to PAMPS. However, for poly(VP‐co‐AMPS), selectivity for nickel ions was observed, and the retention of copper and cadmium ions increased compared to PVP. The homopolymer mixture containing PAMPS and PVP was inefficient for the retention of the studied metal ions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41272.     

Synthesis and characterization of cation‐exchange membrane based on sulfonated sty/HEA/LMA terpolymer

A cation‐exchange membrane based on a styrene/hydroxyethyl acrylate/lauryl methacrylate (Sty/HEA/LMA) terpolymer was prepared via a postsulfonation reaction for various sulfonation times. Sulfonic groups were introduced into the membrane structure with sulfuric acid as the sulfonating agent and silver sulfate as an initiator in a nitrogen atmosphere. Sulfonated Sty/HEA/LMA terpolymer membranes were characterized by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance as well as by determining the degree of sulfonation (DS), ion‐exchange capacity (IEC), water uptake (WU), and electrical property of the membranes. The presence of sulfonic groups in the sulfonated Sty/HEA/LMA terpolymer was confirmed by FTIR, and the resulting membrane showed an IEC of 1.29 meq/g and an electrical resistance of 0.1 Ω cm². The WU of the prepared membranes increased with the DS at the reaction time. The surface morphology obtained by atomic force microscopy clearly showed an increase of roughness with reaction time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of reinforced acrylic‐based superabsorbents crosslinked with divinylbenzene

A series of superabsorbent polymers were synthesized by an inverse suspension polymerization, with potassium persulfate as the initiator, Span60 as the dispersant, and N,N′‐methylene bisacrylamide (BIS) and divinylbenzene (DVB) as multiple crosslinkers. The synthesis conditions, including the amount of dispersant, concentration of crosslinkers, oil‐to‐water phase ratio (O/W) of the polymerization system, total monomer concentration, and acrylamide (AM) content were studied. The results indicated that there were optima for the following properties: BIS crosslinker concentration (0.075 wt %), O/W (3 : 1), total monomer concentration (37.5 wt %), and AM content (5 wt %). In addition, the particle size had a significant influence on the absorption speed, and the absorption speed increased with decreasing particle size. In comparison with the conventional sample crosslinked only by BIS, the superabsorbent with the same particle size but crosslinked by multiple crosslinkers had the higher absorption rate because of surface crosslinking. It also showed that the salt resistance and antihydrolyzing property of the superabsorbent crosslinked by multiple crosslinkers (BIS and DVB) were enhanced, which was also attributed to surface crosslinking by DVB. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1594–1600, 2006     

Synthesis and characterization of a soybean oil‐based macromonomer

An acrylate‐functional soybean oil‐based macromonomer (SoyAA‐1) was synthesized in high yields utilizing sequential amidation and acrylation processes to serve as an internal plasticizer in emulsion polymers. The structure and structure–property relationships of this unique macromonomer were validated with FTIR, NMR, and LC‐MS. The viability of SoyAA‐1 as a comonomer in emulsion polymerization was established via copolymerization with methyl methacrylate (MMA) at varying copolymer weight compositions. The effect of increasing SoyAA‐1 levels and concomitantly higher allylic functionality was measured through film coalescence, minimum film forming temperature, and initial and progressively increasing glass transition temperature(s). The results indicate that synthetic modification of a renewable resource, soybean oil, can yield a valuable monomer that can be copolymerized in high yields via emulsion polymerization to produce practical and mechanically stable latexes for a variety of coatings applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40249.     

Synthesis and characterization of a novel high‐oil‐absorbing resin

A high‐oil‐absorbing resin, which was a low crosslinking resin, was synthesized by conventional suspension copolymerization in this study. The effects of the monomer ratio, crosslinker, initiator, ratio of water to oil, and defined optimum reaction conditions were studied. The highest oil absorptivity of the resin was about 11.5 g/g in diesel and the oil‐absorption saturation time was 3 days when the best process conditions were as follows: ratio of styrene to ethylene–propylene–diene terpolymer = 40/60 w/w, amount of crosslinker divinylbenzene = 1.0 wt %, amount of benzoyl peroxide = 1.0 wt %; proportion of gelatin to calcium phosphate = 0.2 g/0.1 g, stirring speed = 500 r/min, and proportion of water to oil = 15 : 1. By using such methods as infrared spectroscopy, thermogravimetric analysis, and other methods, we studied the oil‐absorbing resin structure, oil‐absorption rate, oil‐absorption saturation time, and oil‐absorption rate twice. The oil‐absorbing resins were used repeatedly through the extraction of ethanol. The experiment results show little effect on the oil‐absorption properties. The oil‐absorption rate constant was evaluated for diesel, and the oil‐absorbing process obeyed the first‐order kinetics equation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly[methyl methacrylate‐co‐2‐ethylhexyl acrylate‐co‐poly(propylene glycol diacrylate)] latices

The emulsion polymerization of the monomers methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) was studied to investigate the effect of the crosslinkable monomer poly(propylene glycol diacrylate) (PPGDA). IR spectroscopy, NMR, differential scanning calorimetry, gel permeation chromatography, and scanning electron microscopy were used to characterize the synthesized polymers. These polymers were coated on glass panels and cured at appropriate temperatures to study the physical properties, swelling behavior, surface tension, and contact angle of these polymer latices. The results show that as the concentration of EHA monomer increased, the surface tension of the latices decreased. The copolymers were characterized by ¹H‐NMR spectroscopy to ensure the absence of unreacted monomer, and the results confirm the incorporation of EHA units in the copolymer. The contact angle of the latices on the glass substrate was smaller than that on the metal. The swelling mechanism of the film showed that the Fickian diffusion coefficient with 10 wt % PPGDA was at a minimum value and was the most highly crosslinked polymer among the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Physicochemical properties and fracture behavior of soy‐based resin

A soy‐based resin was prepared by the process of transesterfication and epoxidation of regular food‐grade soybean oil. The soy‐based resin was used as a reactive diluent and also as a replacement of bisA epoxy resin in an anhydride‐cured polymer. The curing efficiency of soy epoxy resin was studied using differential scanning calorimetry. Physicochemical properties and fracture behavior of soy‐based resin polymers were studied using dynamic mechanical analysis and fracture toughness measurements, respectively. Toughness measurements were carried out using the compact tension geometry following the principles of linear elastic fracture mechanics. Tests showed that the addition of soy‐based epoxy resin to the base epon resin improved the toughness of the blend. Morphology of the fractured specimens has been analyzed by scanning electron microscopy. The soy‐based resins hold great potential for environmentally friendly, renewable resource based, and low cost materials for structural applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Polyurethane‐modified epoxy resin: Solventless preparation and properties

A polyurethane‐modified epoxy resin system with potential as an underfill material in electronic packaging and its preparation procedure were studied. The procedure enabled the practical incorporation of an aliphatic polyurethane precursor, synthesized from poly(ethylene glycol) and hexamethylene diisocyanate without a solvent, as a precrosslinking agent into a conventional epoxy resin. With a stoichiometric quantity of the polyurethane precursor added to the epoxy (ca. 5 phr), the polyurethane‐modified epoxy resin, mixed with methylene dianiline, exhibited a 36% reduction in the contact angle with the epoxy–amine surface, a 31% reduction in the cure onset temperature versus the control epoxy system, and a viscosity within the processable range. The resultant amine‐cured thermosets, meanwhile, exhibited enhanced thermal stability, flexural strength, storage modulus, and adhesion strength at the expense of a 5% increase in the coefficient of thermal expansion. Exceeding the stoichiometric quantity of the polyurethane precursor, however, reduced the thermal stability and modulus but further increased the coefficient of thermal expansion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,characterization, and polymerization of a novel benzoxazine based on diethyltoluenediamine

A novel aromatic diamine‐based benzoxazine monomer (PDETDA) was successfully prepared from diethyltoluenediamine (DETDA), phenol, and paraformaldehyde through a simple one‐step solvent‐less method. The structure of PDETDA was confirmed by FTIR, ¹H NMR, and ¹³C NMR. The curing behavior of PDETDA was studied by DSC, FTIR, and rheological measurement. The results showed that the alkyl substituents on the benzene ring in DETDA not only facilitated the synthesis of PDETDA by effectively hindering the formation of triazine network, but also endowed PDETDA with the advantage of low viscosity (1 Pa s at 90°C). However, steric hindrance of the substituents made PDETDA difficult to form a crosslinked network through ring‐opening polymerization, and therefore only oligomers and noncrosslinked polymers were obtained. The curing kinetics of PDETDA was studied by nonisothermal DSC, and the results revealed that the curing of PDETDA displayed autocatalytic characteristic. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41920.     

Chelation ion‐exchange properties of copolymer resin derived from 4‐hydroxyacetophenone,oxamide, and formaldehyde

A copolymer (4‐HAOF) prepared by condensation of 4‐hydroxyacetophenone and oxamide with formaldehyde in the presence of an acid catalyst proved to be a selective chelating ion‐exchange copolymer for certain metals. Chelating ion‐exchange properties of this copolymer were studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions. A batch equilibrium method was employed in the study of the selectivity of metal‐ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe³⁺ ions than for Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Ni²⁺, and Hg²⁺ ions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 787–790, 2003     

Terpolymer resin II: Synthesis,characterization, and ion‐exchange properties of 2,4‐dihydroxyacetophenone–dithiooxamide–formaldehyde terpolymers

Terpolymers have been prepared by the condensation of 2,4‐dihydroxyacetophenone (2,4‐HA) and dithiooxamide (D) with formaldehyde (F) in the presence of hydrochloric acid as catalyst with varying the molar proportions of the reactant. Compositions of the terpolymer have been determined by elemental analysis. The number average molecular weight has been determined by conductometric titration in nonaqueous medium. Intrinsic viscosities of the solution of the terpolymer have been determined in N,N‐dimethyl formamide (DMF). The terpolymers have been characterized by UV–visible, IR, and proton NMR spectra. Chelation ion‐exchange properties have also been studied employing the batch equilibrium method. It was employed to study selectivity of metal ion uptake over a wide pH range and in media of various ionic strength. The overall rate of metal uptake follows the order: Fe³⁺ > Cu²⁺ > Ni²⁺ > Co²⁺ = Zn²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of methacrylated star‐shaped poly(lactic acid) employing core molecules with different hydroxyl groups

A set of novel bio‐based star‐shaped thermoset resins was synthesized via ring‐opening polymerization of lactide and employing different multi‐hydroxyl core molecules, including ethylene glycol, glycerol, and erythritol. The branches were end‐functionalized with methacrylic anhydride. The effect of the core molecule on the melt viscosity, the curing behavior of the thermosets and also, the thermomechanical properties of the cured resins were investigated. Resins were characterized by Fourier‐transform infrared spectroscopy, ¹³C‐NMR, and ¹H‐NMR to confirm the chemical structure. Rheological analysis and differential scanning calorimetry analysis were performed to obtain the melt viscosity and the curing behavior of the studied star‐shaped resins. Thermomechanical properties of the cured resins were also measured by dynamic mechanical analysis. The erythritol‐based resin had superior thermomechanical properties compared to the other resins and also, lower melt viscosity compared to the glycerol‐based resin. These are of desired characteristics for a resin, intended to be used as a matrix for the structural composites. Thermomechanical properties of the cured resins were also compared to a commercial unsaturated polyester resin and the experimental results indicated that erythritol‐based resin with 82% bio‐based content has superior thermomechanical properties, compared to the commercial polyester resin. Results of this study indicated that although core molecule with higher number of hydroxyl groups results in resins with better thermomechanical properties, number of hydroxyl groups is not the only governing factor for average molecular weight and melt viscosity of the uncured S‐LA resins. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45341.     

Synthesis and properties of acrylic‐based superabsorbent

Acrylic‐based superabsorbent polymers with partial‐neutralized acrylic acid were synthesized by inverse suspension polymerization. The effects of reaction parameters, including the concentration of crosslinking agent and initiator, the neutralization degree of monomer, the monomer concentration, and phase ratio of a system, on the water absorption have been investigated. Furthermore, to improve the properties of salt‐resistance and antielectrolyte for the polymer, acrylamide monomer containing nonionic and hydrophilic groups was introduced into the system, which can suppress the salt effect and homoion effect. The water absorption Q^5/3 is proportional to the reciprocal of ionic strength, 1/S, which follows Flory's elasticity gel theory. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 619–624, 2004     

Physical and potentiometric properties of polyurethane‐based cation‐selective membranes

Lipophilic salts based on tetraphenylborate derivatives [e.g., potassium tetrakis(p‐chlorophenyl)borate (KTpClPB), sodium tetraphenylborate (NaTPB), and cesium tetrakis(3‐methylphenyl)borate are essential ingredients used in the preparation of solvent polymeric cation‐selective membranes. The effects of such lipophilic salts on the physical properties of a polyurethane (PU) matrix comprising 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol, and poly(tetramethylene ether glycol) were examined. Differential scanning calorimetry measurements revealed that the sodium and potassium salts doped in PU increased the glass‐transition temperatures (T_g) of the matrix, while the film containing cesium salt exhibited slightly decreased T_g. The temperature dependence of the ionic conductivity for PU60 films doped with KTpClPB is well described by the Arrhenius‐type equation, and that doped with NaTPB is described by the Vogel–Tammann–Fulcher (VTF)‐type equation. The temperature dependence of the ionic conductivity on the VTF‐type equation suggests that the transport of sodium ions in the PU60 matrix is more strongly coupled to the soft segmental motion, and potassium ions are decoupled from the polymer host and transported by activated hopping. The effect of added salt on the internal structure of PU membranes was investigated by measuring the ratio between the free and hydrogen‐bonded CO bands at 1703 and 1730 cm⁻¹, respectively. The results showed that the ether oxygens in the soft segment chains are strongly coupled to the potassium or sodium, but much less to cesium. The potentiometric properties of these lipophilic additive doped PU membranes were characterized by incorporating valinomycin and 4‐tert‐butylcalix[4]arene‐tetraacetic acid tetraethylester as potassium‐ and sodium‐selective ionophores, respectively. Their response behavior could be explained by the observed physical characteristics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 618–625, 2001     

Synthesis and characterization of soluble hyperbranched polymer via initiator‐fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′‐azobisisobutyrate

The homopolymerization of divinylbenzene (DVB) as an excellent crosslinker (0.20 mol/L) with dimethyl 2,2′‐azobisisobutyrate (MAIB) proceeded homogeneously without any gelation at 80°C in benzene when the MAIB concentrations as high as 0.30–0.50 mol/L were used, yielding soluble polymers. In the polymerization at the concentrations of [DVB] = 0.20 mol/L and [MAIB] = 0.50 mol/L, the polymer yield increased with time and leveled off over 90 min. The molecular weight and molecular weight distribution increased with polymer yield. The vinyl groups of DVB were observed to be almost completely consumed in about 80 min, by FT near‐IR spectroscopic analysis. The homogeneous polymerization system involved ESR‐observable polymer radical, the concentration of which increased with time up to 3.4 × 10^?5 mol/L. The polymer formed in the polymerization for 2 h consisted of 46 mol % of DVB unit and 54 mol % of the methoxycarbonylpropyl group as MAIB fragment, indicating that an initiator‐fragment incorporation radical polymerization proceeds in the present polymerization. The polymer was soluble in benzene, tetrahydrofuran, ethyl acetate, chloroform, acetone, and N,N‐dimethylformamide, while it was insoluble in n‐hexane, acetonitrile, dimethyl sulfoxide, methanol, and water. The results of the multiangle laser light scattering and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched polymer nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 664–670, 2006     

Pore structure of water‐wettable hydrophobic resins based on divinylbenzene and methyl acrylate

Hydrophobic, but water‐wettable porous resins based on divinylbenzene (DVB) and methyl acrylate (MA) were prepared with a wide range of pore structures by suspension copolymerization under different conditions. By using purified DVB (98.8%), the specific surface area for the resulting MA/DVB resins could reach high values at high DVB levels, while these resins are wettable by direct contact with water. An increased content of MA significantly increases the porosity of the resins, whereas the solvating power of the porogen affects both pore structure and water‐wettability of the MA/DVB resins profoundly. Treating these MA/DVB resins with ferric chloride in the presence of dichloroethane gives products with larger surface areas and an enhanced water‐wettability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2681–2688, 2004     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.