Thermoreversible hydrogels. XVIII. Synthesis,swelling characteristics,and diffusion behaviors of porous,ionic, thermosensitive hydrogels

Porous, ionic, thermosensitive hydrogels were prepared from N‐isopropylacrylamide, a cationic monomer [trimethyl (acrylamido propyl) ammonium iodide (TMAAI)], an anionic monomer [acrylic acid (AA)], a zwitterionic monomer [N′,N′‐dimethyl (acrylamido propyl) ammonium propane sulfonate], or a nonionic monomer [poly(ethylene glycol) methyl ether acrylate], and a pore‐forming agent [poly(ethylene glycol) (PEG)] of different molecular weights. Some fundamental properties and dynamic swelling kinetic parameters and solute permeation for these porous gels were investigated. The results showed that the gel containing the cationic monomer TMAAI had a higher equilibrium swelling ratio. The diffusion coefficients showed that the swelling rates for the gels with the anionic monomer AA and PEG with a higher molecular weight (20,000) were faster. The results showed that the fast swelling–deswelling behavior for the porous structure gels was due to them being more available than the gels with long hydrophilic side chains. In addition, the interactive force between the solutes and gels and the solute permeation through the porous gels were investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2214–2223, 2003     

Effect of porosigen and hydrophobic monomer on the fast swelling–deswelling behaviors for the porous thermoreversible copolymeric hydrogels

A series of porous thermoreversible copolymeric hydrogels were prepared from N‐isopropylacrylamide (NIPAAm) and hydrophobic monomers such as 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (OFPMA) and n‐butyl methacrylate (BMA) and CaCO₃ or poly(ethylene glycol) 8000 (PEG8000) as porosigen by emulsion polymerization. The effect of hydrophobic monomers and porosigens on the fundamental properties, such as equilibrium swelling ratio, swelling kinetics, gel strength, crosslinked densities, etc., and fast swelling–deswelling behavior for the present copolymeric hydrogels were investigated. Results showed that the deswelling rates for the gels porosigened by CaCO₃ were more rapid than those gels foamed by PEG8000. Results also showed that the swelling rates for the gel foamed by CaCO₃ were higher than those for the gel foamed by PEG8000. At the same time, results also showed that the gels with OFPMA foamed by CaCO₃ exhibit a faster swelling–deswelling behavior than those gels with BMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3152–3160, 2006     

Swelling–deswelling kinetics of poly(N‐isopropylacrylamide) hydrogels formed in PEG solutions

A series of poly(N‐isopropylacrylamide) (PNIPA) hydrogels was prepared by free‐radical crosslinking copolymerization of N‐isopropylacrylamide (NIPA) and N,N′‐methylenebisacrylamide (BAAm) in aqueous solutions of poly(ethylene glycol) of molecular weight 300 g/mol (PEG). The amount of PEG in the polymerization solvent, the crosslinker (BAAm) content, and the gel preparation temperature (T_prep) were varied in the gelation experiments. The hydrogels were characterized by the equilibrium swelling and elasticity tests as well as by the measurements of the deswelling–reswelling kinetics of the hydrogels in response to a temperature change between 25 and 48°C. The rate of deswelling of the swollen gel increases while the rate of reswelling of the collapsed gel decreases as the amount of PEG in the polymerization solvent is increased or as the crosslinker content is decreased. The T_prep effect on the swelling kinetics of the hydrogels was only observed if the PEG content of the polymerization solvent is less than 20%, which is explained with the screening of H‐bonding interactions in concentrated PEG solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 37–44, 2006     

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     

Preparation and properties of modified PHEMA hydrogel with sulfonated PEG graft

A novel poly(ethylene glycol) (PEG) macromer with a methacryloyl and sulfonic acid group at each end of the chain was prepared. Modified hydroxyethyl methacrylate (HEMA) based hydrogels were synthesized by crosslinking polymerization of HEMA in the presence of the above‐mentioned PEG macromer. The effect of the sulfonated PEG graft was examined by comparing the swelling properties with those of a pure poly(hydroxyethyl methacrylate) (PHEMA) hydrogel. The modified PHEMA hydrogel exhibited increasing water absorbency with increasing sulfonated PEG content up to 15 wt %. These hydrogels with the sulfonated PEG graft exhibited a more hydrophilic character than the pure PHEMA gel. Also the swelling degree varied slightly with pH, showing increased swelling at higher pH probably due to the presence of the anionic sulfonate group on the PEG end chain. In addition, the protein adsorption test showed a lower level of fibrinogen adsorption from the sulfonated poly(ethylene glycol) (SPEG) modified gel than on the homo PHEMA hydrogel. Interestingly, scanning electron microscopy showed that the porous and rather uniform morphology of the gels changed with increasing sulfonated PEG content in PHEMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2484–2489, 2007     

Temperature‐responsiveness and sustained delivery properties of macroporous PEG‐co‐PNIPAAm‐co‐PCL hydrogels

A series of novel thermosensitive macroporous poly (ethylene glycol) (PEG)‐co‐poly(N‐isopropylacrylamide) (PNIPAAm)‐co‐poly (ε‐caprolactone) (PCL) hydrogels were synthesized via in situ free radical polymerization. Poly(ethylene glycol diacrylate) (PEGDAc) and poly(ε‐caprolactone diacrylate) (PCLDAc) were prepared as macrocrosslinkers. All compounds were investigated by Nuclear Magnetic Resonance (NMR) and Fourier transform‐infrared spectroscopy (FT‐IR). Differential Scanning Calorimetry (DSC) results showed the lower critical solution temperatures (LCSTs) of the gels were at around 31°C. The macroporous gels not only had considerable swelling ratios, but also exhibited rapid swelling kinetics and response sensitivity. Above mentioned hydrogels showed a remarkable oscillatory swelling–deswelling transition, making them have potential application in long‐term drug delivery. POLYM. ENG. SCI., 55:223–230, 2015. © 2014 Society of Plastics Engineers     

Hydrophobic association and temperature and pH sensitivity of hydrophobically modified poly(N‐isopropylacrylamide/acrylic acid) gels

Hydrophobically modified poly(acrylic acid/N‐isopropylacrylamide) gels were synthesized by the radical copolymerization of acrylic acid/N‐isopropylacrylamide with a small amount of the hydrophobic comonomer 2‐(N‐ethylperfluorooctanesulfoamido)ethyl acrylate, stearyl acrylate, or lauryl acrylate in tert‐butanol with ethylene glycol dimethacrylate as a crosslinker. Swelling kinetics and fluorescence measurements showed that the hydrophobic association ability of fluorocarbon groups was stronger than that of hydrocarbon analogues in modified hydrogels that contained both physical and chemical crosslinking networks. The effects of the fractions and the species of the hydrophobe on the gel swelling and pH and temperature sensitivity were studied. The results indicated that the swelling behavior and pH and temperature sensitivity of the gels were affected by the degree of hydrophobic modification. A hydrogel with a suitable 2‐(N‐ethylperfluorooctanesulfoamido)ethyl acrylate content (0.349 mol %) showed good pH and temperature sensitivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2406–2413, 2003     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of fast responsive thermo‐ and pH‐sensitive poly[(N,N‐diethylacrylamide)‐co‐(acrylic acid)] hydrogels

BACKGROUND: A considerable amount of research has been focused on smart hydrogels that can respond to external environmental stimuli, especially temperature and pH. In this study, fast responsive thermo‐ and pH‐sensitive poly[(N,N‐diethylacrylamide)‐co‐(acrylic acid)] hydrogels were prepared by free radical copolymerization in aqueous solution using poly(ethylene glycol) (PEG) as a pore‐forming agent. RESULTS: Swelling studies showed that the hydrogels produced had both temperature and pH sensitivity. The deswelling kinetics at high temperature demonstrated that the shrinking rates were influenced by the addition of the pore‐forming agent and the amount of acrylic acid in the initial total monomers. The deswelling curves in low‐buffer solutions had two stages. Pulsatile swelling studies indicated that the PEG‐modified hydrogels were superior to the normal ones. These different swelling properties were further confirmed by the results of scanning electron microscopy. CONCLUSION: Such fast responsive thermo‐ and pH‐sensitive hydrogels are expected to be useful in biomedical fields for stimuli‐responsive drug delivery systems. Copyright © 2008 Society of Chemical Industry     

Synthesis of porous poly(N‐isopropylacrylamide) gel beads by sedimentation polymerization and their morphology

Sedimentation polymerization of aqueous solutions of N‐isopropylacrylamide (NIPA) was carried out to prepare porous poly(N‐isopropylacrylamide) (PNIPA) beads. When small amounts of DMF and a radical accelerator were added to the monomer solution, the polymerization proceeded smoothly to give polymer beads with a very narrow size distribution. The rate of swelling of the resulting bead increased with increasing crosslinker content and was also affected by the type of crosslinker used. When amounts higher than 1 mol % N,N′‐methylenebisacrylamide or 3 mol % diethylene glycol diacrylate (DEGDA) were used as a crosslinker, the resulting beads underwent rapid swelling in water at 20°C, reaching the equilibrium within 5 min. A cross‐sectional photograph of a typical dried bead showed that it had a very complex morphology consisting of a large and irregular void, highly porous region, and nonporous region. The swelling rate was directly dependent on the morphology of the beads. PNIPA beads with well‐developed porous areas show a high swelling rate. Although PNIPA beads produced from DEGDA had well‐developed porous structures, they were able to effectively concentrate blue dextran from the dilute aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 842–850, 2007     

Temperature‐responsive characteristics of poly(N‐isopropylacrylamide) hydrogels with macroporous structure

Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol^?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (ν_E) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry     

Poly(N‐isopropylacrylamide‐co‐poly(ethylene glycol))‐acrylate simultaneously physically and chemically gelling polymer systems

In an effort to create an in situ physically and chemically cross‐linked hydrogel for in vivo applications, N‐isopropylacrylamide (NIPAAm) was copolymerized with poly(ethylene glycol)‐monoacrylate (PEG‐monoacrylate) and then the hydroxyl terminus of the PEG was further modified with acryloyl chloride to form poly(NIPAAm‐co‐PEG) with acrylate terminated pendant groups. In addition to physically gelling with temperature changes, when mixed with a multi‐thiol compound such as pentaerythritol tetrakis 3‐mercaptopropionate (QT) in phosphate buffer saline solution of pH 7.4, this polymer formed a chemical gel via a Michael‐type addition reaction. The chemical gelation time of the polymer was affected by mixing time; swelling of the copolymer solutions was temperature dependant. Because of its unique gelation properties, this material may be better suited for long‐term functional replacement applications than other thermo‐sensitive physical gels. Also, the PEG content of this material may render it more biocompatible than similar HEMA‐based precursors in previous simultaneous chemically and physically gelling materials. With its improved mechanical strength and biocompatibility, this material could potentially be applied as a thermally gelling injectable biomaterial for aneurysm or arteriovenous malformation (AVM) occlusion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

A pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40737.     

Preparation and swelling behaviors of porous hemicellulose‐g‐polyacrylamide hydrogels

Novel porous hydrogels were successfully synthesized from hemicelluloses (HCs) and acrylamide (Am) with poly(ethylene glycol) (PEG) as the porogen. The prepared hydrogels were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy (SEM). The results show that the used PEG was not involved in the formation process of the hydrogels, and the HC‐g‐polyacrylamide hydrogels displayed a higher thermal stability than the hemicellulosic polymer. SEM analysis confirmed that the prepared hydrogels had porous structures. The effects of the Am/HC ratio, the amount and molecular weight of PEG and the amount of the crosslinker N,N‐methylene bisacrylamide on the swelling ratio of the prepared hydrogels were investigated in detail. The experimental data were fitted with the exponential heuristic equation and the Schott second‐order dynamic equation. The diffusion of water molecules into the hydrogel network was found to be non‐Fickian in behavior, and the swelling kinetics could be described by the Schott second‐order dynamic equation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of amphiphilic copolymeric gels with enhanced activity of immobilized enzymes in organic media

Novel amphiphilic copolymeric gels were developed to immobilize lipase. NIPA‐co‐PEGMEA gels were prepared by copolymerizing N‐isopropylacrylamide (NIPA) as a thermosensitive and amphiphilic component and poly(ethylene glycol) methyl ether acrylate (PEGMEA) as a hydrophilic component in aqueous media. The gels can absorb organic solvents at temperatures higher than the lower critical solution temperature owing to the thermosensitive and amphiphilic properties of poly(NIPA). The lipase immobilized within the NIPA‐co‐PEGMEA gel, which had a NIPA : PEGMEA composition of 950 : 50 mol/m³, successfully catalyzed the esterification of oleic acid and ethanol without loss of activity during repeated use within 20–40°C. The activity of the immobilized lipase was considerably higher than that of free lipase. The NIPA‐co‐PEGMEA gels provide a structure that allows the immobilized lipase to work actively in an aqueous environment and with the dispersed state of the lipase in the gels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41905.     

Modulating properties of chemically crosslinked PEG hydrogels via physical entrapment of silk fibroin

A variety of polymers of synthetic origins (e.g., poly(ethylene glycol) or PEG) and macromolecules derived from natural resources (e.g., silk fibroin or SF) have been explored as the backbone materials for hydrogel crosslinking. Purely synthetic PEG‐based hydrogels are often chemically crosslinked to possess limited degradability, unless labile motifs are designed and integrated into the otherwise non‐degradable macromers. On the other hand, SF produced by Bombyx mori silkworm can be easily formulated into physical hydrogels. These physical gels, however, are less stable than the chemically crosslinked gels. Here, we present a simple strategy to prepare hybrid PEG‐SF hydrogels with chemically crosslinked PEG network and physically entrapped SF. Visible light irradiation initiated rapid thiol‐acrylate gelation to produce a network composed of non‐degradable poly(acrylate‐co‐NVP) chains, hydrolytically labile thioether ester bonds, and interpenetrating SF fibrils. We evaluated the effect of SF entrapment on the crosslinking efficiency and hydrolytic degradation of thiol‐acrylate PEG hydrogels. We further examined the effect of adding soluble SF or sonicated SF (S‐SF) on physical gelation of the hybrid materials. The impacts of SF or S‐SF inclusion on the properties of chemically crosslinked hybrid hydrogels were also studied, including gel points, gel fraction, equilibrium swelling ratio, and mesh size. We also quantified the fraction of SF retention in PEG hydrogels, as well as the influence of remaining SF on moduli and degradation of chemically crosslinked thiol‐acrylate PEG hydrogels. This simple hybrid hydrogel fabrication strategy should be highly useful in future drug delivery and tissue engineering applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43075.     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Designing crosslinked hyaluronic acid hydrogels with tunable mechanical properties for biomedical applications

This study develops a simple copolymerization/crosslinking technique to control the swelling and mechanical properties of hyaluronic acid‐based hydrogels. Because of the widespread acceptance of poly(ethylene glycol) in biomedical applications, functionalized oligomers of ethylene glycol (EG) were used as comonomers to crosslink methacrylated hyaluronic acid (MHA). The swelling degree, shear and elastic moduli, and fracture properties (stress and strain) of the gels were investigated as a function of the crosslinking oligomer length and reactive group(s). It was hypothesized that acrylated oligomers would increase the crosslink density of the gels through formation of kinetic chains by reducing the steric hindrances that otherwise may limit efficient crosslinking of hyaluronic acid into gels. Specifically, after crosslinking 13 wt % MHA (47% degree of methacrylation) with 0.06 mol % of (EG)_n‐diacrylate, the swelling ratio of the MHA gel decreased from 27 to 15 g/g and the shear modulus increased from 140 to 270 kPa as n increased from 1 to 13 units. The length and functionality (i.e., acrylate vs. methacrylate) of the oligomer controlled the crosslink density of the gels. The significant changes in the gel properties obtained with the addition of low levels of the PEG comonomer show that this method allows precise tuning of the physical properties of hyaluronic acid (HA) gels to achieve desired target values for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42009.     

Influences of the chain structure of PE‐b‐PEG on the properties of PE/PE‐b‐PEG blend membranes prepared by TIPS

In this article, a series of diblock copolymer polyethylene‐b‐ poly(ethylene glycol)s (PE‐b‐PEGs) with various molecular weight of polyethylene segment was blended with linear low‐density PE. The PE/PE‐b‐PEG blend porous membranes with high porosity were obtained by thermally induced phase separation (TIPS) process. The isothermal crystallization kinetics of PE/LP/PE‐b‐PEG blends indicated that the introduction of PE‐b‐PEG could inhibit the growth rate of polyethylene crystals which could increase the pore size and porosity of the membranes. The PE/PE‐b‐PEG blend membranes with PE₁₃₀₀‐b‐PEG₂₂₀₀ showed the largest pore size and porosity due to its crystallization behavior during TIPS. The surface of the membranes became smoother and the morphology of the membranes could be effectively tuned by introducing PE‐b‐PEG. Compared with the PE membrane, the PE/PE‐b‐PEG blend membranes exhibited higher hydrophilicity (the water contact angle decreased from 112° to 84°), water permeability (the permeation flux increased from 80 to 440 L/m² h under 0.1 MPa), rejection performance (completely reject carbon particles in the filtration of carbon ink solution), and fouling resistance (the value of protein adsorption dropped from 0.25 to 0.05 mg/cm²). The hydrophilicity and fouling resistance of PE/PE‐b‐PEG blend membranes increased as the length of PE segment in PE‐b‐PEGs decreased. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46499.