Phase behavior of N‐isopropylacrylamide/acrylic acid copolymer hydrogels prepared with ultrasound

N‐Isopropylacrylamide/acrylic acid copolymer hydrogels were synthesized with ultrasound. The thermoresponsive phase behaviors of gels synthesized with ultrasound (US gels) were investigated and compared with those of gels synthesized in the absence of ultrasound (FR gels). The US gels showed thermoresponsive swelling behavior with a large hysteresis over a wide range of temperatures around its phase‐transition temperature. The hysteresis became larger with an increasing copolymerized acrylic acid content. The US gels were also characterized from the viewpoint of chemical, hydration, and macroscopic physical structures. Little difference was observed in the chemical and hydration structures of the FR gels and US gels. The macroscopic physical structure of the US gels was, however, distinct from that of the FR gels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2449–2452, 2003     

Effect of porosigen on the swelling behavior and drug release of porous N‐isopropylacrylamide/poly(ethylene glycol) monomethylether acrylate copolymeric hydrogels

A series of porous thermoreversible hydrogels were prepared from N‐isopropylacrylamide (90 mol %) and poly(ethylene glycol) methylether acrylate (10 mol %), which was derived from poly(ethylene glycol) monomethylether, N,N′‐methylenebisacrylamide, and porosigen, or poly (ethylene glycol) (PEG) with different molecular weights (MWs). The influence of pore volume in the gel on the physical properties, swelling kinetics, and solute permeation from these porous gels was investigated. The results show that the surface areas, pore volumes, and equilibrium swelling ratios for the porous gels increased with increasing MW of PEG, but the shear moduli and effective crosslinking densities decreased with increasing MW of PEG. The results from the dynamic swelling kinetics show that the transport mechanism was non‐Fickian. The diffusion coefficients of water penetrating into the gels increased with increasing pore volume of the gels. In addition, we also studied solute permeation through the porous gel controlled by temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5490–5499, 2006     

Fast pH‐thermo‐responsive copolymer hydrogels with micro‐porous structures

Micro‐porous copolymer hydrogels were prepared by γ‐ray irradiation of mixed solutions of N‐isopropylacrylamide (NIPAAm) and acrylic acid (AAc) above the lower critical solution temperature (LCST). From Cryo‐SEM observations, the gels were found to consist of three‐dimensional fibrous micro‐gels and micro‐pores. The copolymer gels swelled at temperatures below the LCST and shrunk at temperatures above it, and they showed rapid volume transitions on a time scale on the order of a minute when experiencing temperature changes between 10 and 40°C. The transition times for thermal shrinking were almost the same regardless of AAc composition, but the transition times for thermal swelling were increased with increasing AAc contents. The copolymer gels also showed rapid volume transitions with time constants on the order of an hour on experiencing pH changes between 2 and 12. The transition times for pH volume change at 10°C were within one hour, except for the gels containing only small amounts of AAc. On the other hand, the transition times for pH‐dependent volume change at 40°C were increased with increasing AAc content. The lower responsiveness of the transition results from an increase in hydrophobicity arising from the formation of inter‐ and intra‐molecular hydrogen bonds between the non‐ionized carboxylic acid groups and the amide groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 75–84, 2003     

Effect of the synthesis initiation mode on the structure and properties of sulfadiazine molecularly imprinted polymers

In the presence of imprinting molecules of sulfadiazine, two kinds of molecularly imprinted polymers (MIPs) were synthesized by photoinitiated and thermally initiated polymerizations, respectively. The combination of sulfadiazine and α‐methyl acrylic acid and their composite ratio were studied by differential UV absorption spectrometry. The results show that a combined effect between the functional monomer and the imprinting molecule occurred in the solution. The structure and properties of these synthetic polymers were researched and compared with IR spectroscopy, transmission electron microscopy, and a balanced combination of static experiments. The polymer materials synthesized in these two ways had the same molecular structure, but their morphology was different. Furthermore, through the adsorption isotherm, Scatchard analysis, and evaluation of the imprinting efficiency, we determined that the lower temperature was a more suitable synthesis condition for the polymerization of the MIPs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reentrant phase transition and fast responsive behaviors of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels prepared in poly(ethylene glycol) solutions

Macroporous temperature‐sensitive poly {N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels were synthesized by free‐radical crosslinking polymerization of the monomer N‐[3‐(dimethylaminopropyl)] methacrylamide and the crosslinker N,N′‐methylenebisacrylamide in aqueous solutions at 22°C. Poly(ethylene glycol) (PEG) with a molecular weight of 1000 g/mol was used as the pore‐forming agent during the polymerization reaction. The concentration of PEG in the polymerization solutions was varied between 0 and 18 wt %, whereas the crosslinker (N,N′‐methylenebisacrylamide) concentration was fixed at 2 wt % (with respect to the monomer). The effects of the PEG concentration on the thermo‐induced phase‐transition behavior and the chemical structure, interior morphology, and swelling/deswelling kinetics were investigated. Normal‐type hydrogels were also prepared under the same conditions without PEG. An interesting feature of the swelling behavior of both the normal‐type and macroporous hydrogels was the reentrant phase transition, in which the hydrogels collapsed once and reswelled as the temperature was continuously increased. Scanning electron micrographs revealed that the interior network structure of the hydrogels prepared in PEG solutions became more porous with an increase in the PEG concentration in the polymerization solution. This more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved responsive rate to external temperature changes during the deswelling and swelling processes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

具有快速响应特性的环境响应型智能水凝胶的研究进展

环境响应智能水凝胶应用于化学传感器、化学微阀、人造肌肉、药物控释载体、物质分离等领域时常常需要快速响应特性,提高智能水凝胶的响应速率成为了智能水凝胶研究领域的重要课题之一。本文主要综述了具有快速响应特性的环境响应智能水凝胶的构建策略与方法,重点介绍了3类具有不同结构的快速响应型智能水凝胶,即具有多孔结构的快速响应智能水凝胶、具有梳状结构的快速响应智能水凝胶以及具有微球复合结构的快速响应智能水凝胶。     

Smart carboxymethylchitosan hydrogels that have thermo‐ and pH‐responsive properties

Thermo‐responsive poly(N‐isopropylacrylamide) (poly(NIPAAm)) and pH‐responsive poly(N,N′‐diethylaminoethyl methacrylate) (poly(DEAEMA)) polymers were grafted to carboxymethylchitosan (CMC) via radical polymerization to form highly water swellable hydrogels with dual responsive properties. Ratios of CMC, NIPAAm to DEAEMA used in the reactions were finely adjusted such that the thermo and pH responsiveness of the hydrogels was retained. Scanning electron microscopy (SEM) indicated the formation of an internal porous structure for the swollen CMC hydrogels upon incorporation of poly(NIPAAm) and poly(DEAEMA). Effect of temperature and pH changes on water swelling properties of the hydrogels was investigated. It was found that the water swelling of the hydrogels was enhanced when the solution pH was under basic conditions (pH 11) or the temperature was below its lower critical solution temperature (LCST). These responsive properties can be used to regulate releasing rate of an entrapped drug from the hydrogels, a model drug, indomethacin was used to demonstrate the release. These smart and nontoxic CMC‐based hydrogels show great potential for use in controlled drug release applications with controllable on‐off switch properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41505.     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Porous magnetic chelator support for albumin adsorption by immobilized metal affinity separation

Magnetic poly(2‐hydroxyethylmethacrylate) (mPHEMA) beads are modified by iminodiacetic acid (IDA) to implify the reactive groups and subsequent binding of Cu²⁺ ions to form metal chelate. mPHEMA beads, in the size range of 80–120 μm, were produced by a modified suspension polymerization technique. mPHEMA beads were characterized by swelling tests, electron spin resonance (ESR), FTIR, and scanning electron microscopy (SEM). Important results obtained in this study are as follows. The swelling ratio of mPHEMA beads was 34%. The presence of magnetite particles in the polymeric structure was confirmed by ESR. FTIR data confirmed that the magnetic polymer beads were modified with functional groups IDA. The mPHEMA beads have a spherical shape and porous structure. The effect of pH and concentration of human serum albumin (HSA), on the adsorption of HSA to the metal‐chelated magnetic beads, were examined in a batch reactor. Most importantly, the magnetic beads had little nonspecific adsorption for HSA (0.5 mg/g) before introducing IDA groups. Cu²⁺ chelation increased the HSA adsorption up to 28.4 mg/g. Adsorption behavior can be described at least approximately with the Langmuir equation. Regeneration of the metal‐chelated magnetic beads was easily performed with 1.0M NaSCN, pH 8.0, followed by washing with distilled water and reloading with Cu²⁺. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2501–2510, 2004     

Hydrodynamics and dynamic capacity of cryogels produced with different monomer compositions

Cryogels have received great attention in the area of bioseparation due to their characteristic of very large and interconnected pores. These materials allow rapid isolation of various biomolecules and permit that chromatographic processes are carried out at high flow rates. Nevertheless, studies regarding the effect of monomer concentration on the hydrodynamics and dynamic capacity of cryogels are scarce. In this study, supermacroporous polyacrylamide cryogels with different monomer and crosslinker concentrations were produced by cryopolymerization and activated with tris(hydroxymethyl)aminomethane. Porosity and permeability were determined and it was observed that these parameters changed with different monomer concentrations, indicating changes in the structure of the cryogels. Residence time distribution experiments were conducted at different flow rates and different mobile phase viscosities. As a function of composition of the cryogels, the axial dispersion increased and the flow pattern deviated considerably from the ideal plug flow model. For cryogels with lower crosslinker content, the effect of the mobile phase viscosity was more evident. The monomer composition changed the dispersion number and height equivalent to one theoretical plate, resulting in an impact on the adsorption capacity of the cryogel. Consequently, proper monomer and crosslinker concentrations may produce cryogels with suitable performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48507.     

Coagulation and sedimentation of bacteria using a highly biodegradable polymeric coagulant

Copolymer of acrylamide with N‐benzyl‐4‐vinylpyridinium chloride (PAAM‐co‐BVP) produced coagulation and sedimentation of Escherichia coli, Bacillus subtillus, Pseudomonas aeruginosa, and Staphylococcus aureus. Addition of more than 50 mg L^?1 of PAAM‐co‐BVP produced bacterial flocks that precipitated at a rate of around 200 cm h^?1. Supernatant population reduced in the range 1/30,000–1/25,000,000. Reduction of supernatant population was most effective when about 200 mg L^?1 of PAAM‐co‐BVP was added. PAAM‐co‐BVP was highly biodegradable and the half‐life estimated was 2.4 days when treated with activated sludge. The ratio of biochemical oxygen demand for 5 days (BOD₅) to total organic carbon (TOC) was 0.607. Coagulation and sedimentation of bacteria using PAAM‐co‐BVP is expected to improve the water disinfection processes by saving chlorine and other hazardous chemical fungicides and by reducing the formation of trihalomethanes and other toxic chemical materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1618–1623, 2006     

Influence of 2,2′,6,6′‐tetramethyl biphenol‐based anion‐exchange membranes on the diffusion dialysis of hydrochloride acid

Quaternary ammonium functionalized poly(arylene ether) (QPAE‐Br) membranes based on 2,2′,6,6′‐tetramethyl biphenol for diffusion dialysis (DD) were designed and successfully fabricated via nucleophilic substitution polycondensation, bromination, film casting, and quaternization. The structures, thicknesses, ion‐exchange capacities (IECs), water uptakes, swelling ratios, ion conductivities, and mechanical properties of QPAE‐Br were used to characterize the membranes. The influence of the membrane structures on the DD performances was investigated by DD tests of simulated industrial pickling wastewater (1 mol/L HCl, 0.1 mol/L FeCl₂). The DD results show QPAE‐a (IEC = 1.51 mmol/g) as the best DD candidate. Predialysis treatments further improved the DD performances of QPAE‐Br. QPAE‐a exhibited an excellent proton diffusion coefficient ( ) of 0.033 m/h and a high separation factor (S) of 95.45 after the predialysis treatment at room temperature; these values were much higher than those of the commercial DF‐120B membrane (0.004 m/h for and 24.3 for S at 25 °C) and other reported DD membranes. QPAE‐a has great potential for acid recovery via DD. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45333.     

Polyamide nanofiber membranes functionalized with zinc phthalocyanines

Electrospinning is an efficient method for the production of polyamide nanofiber membranes that are suitable for water filtration. Previous studies have shown that nanofiber membranes have high clean water permeability. The pathogen removal efficiency can be improved by functionalization with (organic) biocides. However, these membranes, like other membranes, are vulnerable to fouling which reduces the filtration efficiency. Therefore the present article investigates the potential of zinc phthalocyanines, which can produce singlet oxygen in the presence of visible light, as a functionalizing agent. The polyamide nanofiber membranes were functionalized with phthalocyanines using both a pre‐functionalizing and post‐functionalizing method. Only the post‐functionalization method shows to result in nanofiber membranes capable of producing singlet oxygen. After 30 min 45% of 1,2‐diphenylisobenzofuran (DPBF), used as an oxygen quencher, was removed by reaction with singlet oxygen. This resulted in a removal rate of 0.33 mol DBPF mol^?1Zn min^?1. During short term leaching tests, phthalocyanines could not be detected. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40486.     

Concentration effect on aggregation and dissolution behavior of poly(N‐isopropylacrylamide) in water

The concentration effect on aggregation and dissolution behavior of poly(N‐isopropylacrylamide) (PNIPAM) in water was studied. Three concentration regimes with different phase behavior were identified by differential scanning calorimetry (DSC). Further optical, light‐scattering, and rheological studies indicated that the appearance of different regimes arose from their corresponding solution structures below lower critical solution temperature (LCST): free chains and small clusters in regime I, large clusters in regime II, and a gel‐like network in regime III. Different solution structures below LCST led to different phase‐separated patterns formed above LCST: colloidal particles in regime I, large precipitate in regime II, and the sponge‐like solid in regime III, which was well understood based on the overlapping parameter P. Different phase‐separated patterns therefore resulted in different remixing behavior as observed by DSC. This work suggests that the swelling and collapse behavior of PNIPAM based hydrogels was controlled through the design of their phase‐separated patterns, and therefore provided a way to develop high performance thermo‐sensitive materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41669.     

Inhibiting the concentration polarization of FO membranes based on the wettable microporous supporting layer and the enhanced dense skin layer

A novel thin film composite‐type forward osmosis (FO) membrane with inhibited concentration polarization phenomenon and expectant separation performance was prepared by continuous interfacial polymerization method. The nylon‐6,6 microfiltration membrane with the average pore size of 5 μm and the self‐wetting property was for the first time used as the supporting layer of the FO membranes, which decreased the mass transfer resistance in the porous supporting layer. The skin layer was prepared via the continuous interfacial polymerization of polyamide as a relatively dense layer, with the reverse salt flux of less than 1 g/m^?2 h^?1. The mass transfer resistance and the reverse salt flux of the prepared FO membranes were remarkably reduced due to the functional design of the double‐layer structure, which effectively enhanced the separation selectivity and restrain the concentration polarization of the FO membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45133.     

Temperature responsive fibers with anisotropic transitional behavior

Temperature sensitive polymer hydrogels are being extensively studied because of their potential applications in the biomedical, robotics, and chemical industries. However, major hurdles in their development have been their slow response, low efficiency (swelling/deswelling ratios), and poor mechanical properties due to difficulty in processing them into mechanically strong and fine structures. Fibers made from such polymers would be highly desirable. A temperature sensitive random linear copolymer of N‐tert‐butylacrylamide (NTBA) and acrylamide (Am) was synthesized by the solution polymerization method, using regulated dosing of comonomers. Using a novel approach, a high molecular weight poly(N‐tert‐butylacrylamide‐ran‐acrylamide::27 : 73) has been converted to insoluble strong fibers with fineness of 30–50 microns by solution spinning, drawing, and subsequent crosslinking. Fibers were solution spun in acetone using a 14% copolymer solution in acetic acid with polycarboxylic acid as a crosslinker and sodium hypophosphite as a catalyst. The crosslinks were formed, subsequent to drawing, between reactive amide side groups of the acrylamide moiety of the polymer and the carboxylic acid group of the crosslinker by thermal treatment at 160°C. The transition temperatures of the crosslinked fibers were found to shift towards the lower temperature from 37°C (in linear copolymer) to 22–25°C. These engineered fibers display sharp temperature sensitivity, extremely high reversible change in dimensions (1000% in diameter and ～ 70% in length), and extremely fast response time (< 20 s for expansion and < 2 s for contraction). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 681–688, 2005     

Synthesis and characterization of new methacrylate-type hydrogels containing 2-tert-butylamino ethyl groups for sorption purposes

Crosslinked poly[2-(tert-butylamino)ethyl methacrylate] (PtBAEMA) hydrogels were synthesized by ⁶⁰Co-γ-radiation-initiated simultaneous polymerization and crosslinking of 2-(tert-butylamino)ethyl methacrylate in bulk and in aqueous solutions. The results showed that the gelation percentage decreased with increasing water content. The structural and thermal characterizations of the hydrogels were accomplished with several techniques, including Fourier transform infrared spectroscopy, swelling measurements, thermogravimetry, and differential scanning calorimetry. The effects of time, pH, temperature, and ionic strength on the swelling behavior were also investigated. Swelling equilibrium was attained in 2–3 days. PtBAEMA hydrogels originally swelled to 350% (by volume) in deionized water, but this value reached 3000% around pH 2.0. PtBAEMA hydrogels were reversibly affected by the change in temperature within the temperature range of 4–70°C. The swelling ratios of the gels decreased with increasing ionic strength. As a result, PtBAEMA hydrogels show stimuli-responsive properties depending on the characteristics of the environment, and they are being considered for adoption as some kind of carrying material for separation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Equilibrium swelling behavior of thermally responsive metal affinity hydrogels, Part I: Compositional effects

Copolymer hydrogels were synthesized from N-isopropylacrylamide (NIPAAm) and vinyl iminodiacetic acid (VIDA) monomers, incorporating thermally responsive swelling and metal affinity properties. Compared to pure NIPAAm hydrogels, the copolymer hydrogels showed significantly increased swelling due to the hydrophilic VIDA groups while still retaining their sharp phase transition behavior. However, excessive amounts of VIDA caused the gels to lose this behavior and not fully collapse even at temperatures as high as 80 °C. When chelated with copper the VIDA groups became less hydrophilic, partially reversing the increased swelling due to VIDA, enabling the gels to regain their phase transition behavior. Increasing the crosslinking density in the gels generally had the effect of decreasing their swelling. However, for gels with higher VIDA amounts, increasing the crosslinking density unexpectedly caused the hydrophilic groups with bound waters to resist the hydrophobic group-induced collapse at high temperatures. The results suggest that the NIPAAm, VIDA and crosslinker amounts and copper chelation are essential elements in the molecular design of the gel to retain a sharp phase transition. These variables were used to develop a phase transition phase diagram.     

Equilibrium swelling behavior of thermally responsive metal affinity hydrogels, Part II: Solution effects

In a previous study the effect of compositional variations on the equilibrium swelling of co-polymer hydrogels designed and synthesized from N-isopropylacrylamide (NIPAAm) and vinyl iminodiacetic acid (VIDA) monomers was investigated [Iyer G, Tillekeratne LMV, Coleman MR, Nadarajah A. Polymer, in this issue, doi:10.1016/j.polymer.2008.06.037]. The gels have both thermally responsive swelling and metal affinity properties and the effect of solution conditions on the equilibrium swelling of copper chelated and unchelated gels is studied here. In contrast to their sharp phase transition behavior in DI water, buffer solutions unexpectedly caused swelling of both gels to be the same and lose the sharp phase transition. Imidazole solutions had the expected phase transition behavior with increasing swelling and loss of phase transition of the unchelated gels which were partially reversed by copper chelation. Other small non-binding molecules, such as phenol, had minimal effects on the swelling behavior. Chicken egg white lysozyme solutions caused both gels to have reduced but equal equilibrium swelling and lose their sharp phase transition. These solution effects are explained in terms of salting in/salting out phenomena, the polarization of amide groups in VIDA, the solution pH and protein adsorption on hydrogel surfaces.     

Facile synthesis of a triptycene-based porous organic polymer with a high efficiency and recyclable adsorption for organic dyes

Water contamination resulting from organic dyes has had severe detrimental effects on human health and environmental tolerance. To address this issue, a delicate strategy for taking host–guest function in porous organic polymers via a facile Friedel–Crafts reaction of triptycene and post-modification was achieved. By means of this route, a sulfonic acid functionalized triptycene-based porous organic polymer (TPOP–SO₃H) with a hierarchical structure and a desirable Brunauer–Emmett–Teller value of 1002 m²/g was synthesized this study. The TPOP–SO₃H material demonstrated a maximum adsorption capacity for methylene blue of 97.1 mg/g. Remarkably, an absorption efficiency of more than 90% of TPOP–SO₃H was observed even after five cycles. Therefore, such a hierarchical porous organic polymer can be highly recommended as one type of promising material for the treatment of organic dye-polluted wastewater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47987.