Preparation and characterizations of interpenetrating polymer network hydrogels of poly(ethylene oxide) and poly(methyl methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(ethylene oxide) and poly(methyl methacrylate) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone and ethylene glycol dimethacrylate as initiators and crosslinkers, respectively. The IPN hydrogels were analyzed for sorption behavior at 25°C and at a relative humidity of 95% using dynamic vapor sorption. The IPN hydrogels exhibited a relatively high equilibrium water content in the range of 13–68%. The state of water in the swollen IPN hydrogels was investigated using differential scanning calorimetry. The free water in the hydrogels increased as the hydrophilic content increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 258–262, 2003     

Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the C?C amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41939.     

Equilibrium Swelling Studies of Chemically Cross-Linked Highly Swollen Acrylamide-Sodium Acrylate Hydrogels in Various Water-Solvent Mixtures

Swelling behavior of acrylamide (AAm)/sodium acrylate (SA) hydrogels was investigated in water-solvent (methanol, ethanol, t-butanol and acetone) mixtures of various compositions. AAm/SA hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with SA as comonomers and a multifunctional cross-linker such as trimethylolpropane triacrylate (TMPTA). Swelling experiments were performed in water and water-organic solvent mixtures of various compositions at 25°C, gravimetrically. The value of S_eq% of AAm/SA hydrogels are 64–152% for 60% of metanol, 84–102% for 60% of ethanol, 127–176% for 60% of t-butanol, 131–585% for 60% of acetone, while the value of S_eq% of AAm/SA hydrogels are 780–4510% for water and water-solvent mixtures. Some swelling kinetic parameters were found. Diffusion behavior of water and water-solvent mixtures was investigated. Diffusion of water and water-solvent mixtures into the hydrogels was found to be non-Fickian in character.     

Graft polymerization of styrene onto starch by simultaneous cobalt-60 irradiation

Starch-g-polystyrene copolymers have been prepared by the simultaneous ⁶⁰Co-irradiation of starch–styrene mixtures, and copolymers have been characterized with respect to weight per cent polystyrene (% add-on) and also the molecular weight and molecular weight distribution of polystyrene grafts. In a typical polymerization, 4 g each of starch and styrene were blended with 1 ml water and 1.5 ml of an organic solvent; the resulting semisolid paste was irradiated to a total dose of 1 Mrad. With ethylene glycol, acetonitrile, ethanol, methanol, acetone, and dimethylformamide as the organic solvent, values for % add-on ranged from 24% to 29%. The highest % add-on (43%) and the highest conversion of styrene to grafted polymer (76%) were obtained when the organic solvent was omitted, and water alone was used. When water was also omitted, polymerization of styrene was negligible; however, graft copolymer was formed in the absence of water when either ethylene glycol or ethanol was added. Attempts were unsuccessful to achieve a % add-on greater than 43% by doubling the amount of styrene in the polymerization recipe. Mixtures of equal weights of starch and styrene are relatively nonvicious, but these mixtures thicken when either water or ethylene glycol is blended in. Reasons for this thickening action and the possible influence of thickening on the graft polymerization reaction were explored.     

Dye Sorption and Water Uptake Properties of Crosslinked Acrylamide/Sodium Methacrylate Copolymers and Semi-Interpenetrating Polymer Networks Composed of PEG

A series of novel semi-interpenetrating polymer networks hydrogels composed of poly(ethylene glycol) and random copolymer of acrylamide/sodium methacrylate were prepared by polymerization of aqueous solution of acrylamide, sodium methacrylate using ammonium persulphate/N,N,N′,N′-tetramethylethylenediamine as a redox-initiating pair in the presence of poly(ethylene glycol) and poly(ethylene glycol)diacrylate as crosslinker. Fourier Transform Infrared spectroscopy was used to identify the presence of different repeating units in the semi IPNs. Water uptake and dye-sorption properties of acrylamide/sodium methacrylate hydrogels and acrylamide/sodium methacrylate/poly(ethylene glycol) semi IPNs were investigated as a function of chemical composition of the hydrogels. Cationic dye, Janus Green B have been used in sorption studies as a model molecule. This study has given the quantitative information on the swelling and sorption characteristic of acrylamide/sodium methacrylate hydrogels and acrylamide/sodium methacrylate/poly(ethylene glycol) semi IPNs in many potential applications.     

Poly(ethylene glycol)‐containing cationic hydrogels with lipophilic character

Not much effort has been focused towards the development of hydrogels that swell in nonpolar solvents. We have synthesized a new set of polyelectrolyte hydrogels and demonstrated their ability to absorb a less‐polar or nonpolar organic solvent, as well as their ability to resist gel‐collapse in a predominantly nonpolar medium. The hydrogels were prepared by free radical polymerization of different molar ratios of poly(ethylene glycol) methyl ether acrylate and (3‐(methacryloylamino)propyl)‐trimethyl ammonium chloride as comonomers in an aqueous medium. Their swelling behavior in organic solvents was studied by varying the dielectric constant of the swelling medium including mixed‐solvent systems. Besides a high degree of swelling (up to 200 times) in polar solvents, some of the hydrogels also exhibited moderate swelling (up to 15 times) in less‐polar organic solvents. Hydrogels samples with high cationic content showed drastic change in swelling extent in some of the mixed‐solvent systems. It was also interesting to note that the retention of significant swelling in dimethyl sulphoxide–toluene mixture with even 90% toluene content for some compositions. These polyelectrolyte hydrogels with improved lipophilicity opens up greater opportunities for the development of even superior soft materials through proper structural optimizations that would successfully function for a wider range of solvents. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39873.     

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     

Swelling behavior of physical and chemical DNA hydrogels

DNA hydrogels were prepared from aqueous solutions of double‐stranded DNA (about 2000 base pairs long) by physical and chemical means. Physical gels were obtained via denaturation–renaturation cycle of 5% aqueous DNA solutions between 25 and 90°C. Although physical DNA gels exhibit a high modulus of elasticity, the crosslinks holding the DNA network together are destroyed during the expansion of gels in water or in dilute salt solutions. It was shown that these gels can be used for the controlled release of DNA in aqueous media. Chemical DNA gels formed using ethylene glycol diglycidyl ether crosslinker are stable in water with a wide range of swelling ratios that could be adjusted by the amount of DNA at the gel preparation. Swelling behavior of chemical DNA gels in acetone/water mixtures as well as in aqueous salt solutions is very similar to that of synthetic polyelectrolyte hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Solvent-, ion- and pH-specific swelling of poly(2-acrylamido-2-methylpropane sulfonic acid) superabsorbing gels

Homopolymer hydrogel of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and its nanocomposite counterpart were prepared to study their swelling properties. The hydrogels showed ability to absorb and retain electrolytes as well as binary mixtures of water and organic solvents (i.e., methanol, ethanol, acetone, ethylene glycol (EG), polyethylene glycol, N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The nanocomposite gel exhibited lower swelling in all solvent compositions in comparison with non-composite gel. Unlike conventional acrylic acid-based hydrogels, the poly(AMPS) gels showed superabsorbing capacity in pure ethanol, methanol, EG, DMSO and NMP. Meanwhile, swelling capacity of poly(AMPS) hydrogel in DMSO-water mixtures was surprisingly found to be even higher than that in water. This extraordinary superswelling behavior was explained based on the interactions involved in solvation as well as the solubility parameters. The gels showed pH-independent superabsorbency in a wide range of pH (3–11). Saline-induced swelling transitions were also investigated and the ionic interactions were confirmed by FTIR spectroscopy.     

Novel Biodegradable pH/Thermosensitive Hydrogels: Part 1. Preparation and Characterization

A series of biodegradable and pH/thermosensitive hydrogels based on monomethoxyl poly(ethylene glycol) (MPEG), poly(?-caprolactone) (PCL), methylacrylic acid (MAA), and N-Isopropylacrylamide (NIPAAm) were prepared by UV-initiated free radical polymerization method. Swelling behavior and hydrolytic degradable behavior in aqueous medium with different pH values and pH/thermosensitivity of the hydrogels were studied in detail. The prepared biodegradable pH/thermo-sensitive hydrogels based on PCL, MPEG, MAA, and NIPAAm may have great potential application in smart drug delivery system.     

Biodegradable Inorganic–Organic POSS–PEG Hybrid Hydrogels as Scaffolds for Tissue Engineering

Biodegradable hydrogels have attracted much attention in tissue engineering due to their good biocompatibility and elastomeric behavior. In this work, a series of inorganic–organic polyhedral oligomeric silsequioxanes–poly(ethylene glycol) (POSS–PEG) hybrid hydrogels are prepared by covalently grafting POSS into PEG and further cross‐linked by matrix metalloproteinase (MMP) degradable peptide via Michael‐type addition polymerization. All the POSS–PEG hybrid hydrogels have a porous structure and high hydrophilic ability, and the grafted hydrophobic POSS macromers result in a higher mechanical properties and lower equilibrium swelling ratio. Additionally, the hydrogels can be biodegraded by MMP‐2 solution and the POSS loading level can influence the degradation rate. It is worth mentioning that POSS‐containing hybrid hydrogels can be prepared in water and be used for 3D cell culture. In vitro cell viability study on human umbilical vein endothelial cells for 3D cell culture indicates POSS–PEG hydrogels have good compatibility. All of these results suggest that these POSS–PEG hybrid hydrogels exhibit the potential for tissue engineering scaffolds.     

3D Printing/Interfacial Polymerization Coupling for the Fabrication of Conductive Hydrogel

In this study, 3D printing is coupled with interfacial polymerization to obtain electroactive hydrogels with complex and defined geometry. Conductive hydrogels are created through a two‐step procedure: first a digital light processing 3D printing system is used to fabricate poly(ethylene glycol)diacrylate 3D structure and then pyrrole is oxidized to polypyrrole (PPY), exploiting an interfacial polymerization mechanism through which PPY can be formed in the poly(ethylene glycol) matrix, thus creating a conductive phase.     

Synthesis and characterization of ABA triblock and novel multiblock copolymers from ethylene glycol,L‐lactide,and ϵ‐caprolactone

Three types of copolymers were synthesized and characterized. First, triblock ABA copolymers [where A is a homopolymer of ?‐caprolactone and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with ?‐caprolactone in the presence of stannous octoate (Sn(Oct)₂). The spectral, thermal, and mechanical properties of one sample of these copolymers were studied, and it was discovered that these types of copolymers were more hydrophilic, possessed lower melting points, and had superior mechanical properties (greater toughness) than poly(?‐caprolactone). Second, triblock ABA copolymers [where A is a homopolymer of L ‐lactide and B is poly(ethylene glycol)] were prepared by the ring‐opening polymerization of poly(ethylene glycol) with L ‐lactide in the presence of Sn(Oct)₂. The mechanical properties of these copolymers were studied, and it was found that they were tougher and softer than poly(L ‐lactide). Third, novel ABA triblock copolymers [where A is a copolymer of ?‐caprolactone and L ‐lactide and B is poly(ethylene glycol)] were prepared, and ¹H‐NMR and ¹³C‐NMR spectra of these copolymers indicated a microblock structure for the two end blocks. The stress–strain behavior revealed low yields and high toughness for these copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2072–2081, 2002     

Swelling Characterization and Adsorptive Features of Acrylamide/Itaconic Acid Hydrogels and Semi-IPNs for Uranyl Ions

A novel semi-interpenetrating network (semi-IPNs) hydrogel, composed of acrylamide (AAm) with itaconic acid (ITA) as co-monomer, with poly (ethylene glycol)(PEG) and trimethylolpropane triacrylate (TMPTA) was prepared. Hydrogels and semi-IPNs were synthesized by free radical solution polymerization. Swelling experiments were performed in water and aqueous solutions of uranyl acetate. Diffusion behavior was investigated and their diffusion into hydrogels was found to be non-Fickian in character. Sorption of uranyl ion onto the polymeric system was studied by a batch sorption technique at 25°C. The sorption capacity, removal effiency and partition coefficient of the hydrogels were investigated.     

Synthesis and characterization of acrylamide and 2‐hydroxylpropyl methacrylate hydrogels for specialty applications

To modify acrylamide (AAm) hydrogels for specialty applications, it was copolymerized with 2‐Hydroxypropyl methacrylate (HPMA) in different molar ratio at 25°C in 1:1 water–acetone solvent system, using ammonium persulphate (APS) and N,N,N,N‐tetramethyl ethylene diamine (TEMED) initiator–accelerator system. Two series of hydrogels were thus prepared using two different crosslinkers—ethylene glycol dimethacrylate (EGDMA) and N,N‐methylene bisacrylamide (N,N‐MBAAm). To affect property profile of the hydrogels, concentration of HPMA was varied over a range of five concentrations from 3.5 to 28 mM. Hydrogels were further functionalized by partial hydrolysis with NaOH and Hofmann amide degradation reaction. FTIR, Nitrogen analysis, and SEM were used to establish monomer reactivity and structure relationship of the hydrogels. Metal ion uptake was studied as a function of various structural aspects of the hydrogels. Water uptake behavior of the hydrogels was studied at constant time, temperature, and pH, both pre and post metal loading. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3040–3049, 2006     

Immobilization of myoglobin from horse skeletal muscle in hydrophilic polymer networks

This work examines the immobilization of myoglobin from horse skeletal muscle in hydrophilic polymer networks. Due to specific changes in the spectroscopic properties of hemoproteins during ligand binding, they could be employed in optical sensing devices. Two immobilization techniques were considered: imbibition and entrapment. Anionic hydrogels composed of methacrylic acid (MAA), cationic hydrogels composed of dimethylamino ethyl methacrylate (DMAEM), and neutral hydrogels composed of poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMA; molecular weight = 200, 400, or 1000), all crosslinked with poly(ethylene glycol) dimethacrylate (PEGDMA) (molecular weight = 200, 600, or 1000), were synthesized by free‐radical solution polymerization. By the imbibition method, MAA‐based hydrogels incorporated the highest amount of myoglobin in comparison with PEGMA or DMAEM polymers. The evaluation of the correlation length of the networks revealed that MAA hydrogels had the highest correlation length in comparison with PEGMA‐containing matrices or DMAEM hydrogels. Release experiments from MAA hydrogels at pHs 5.8 and 7.0 showed that the solute‐transport mechanism was a combination of Fickian and chain relaxation diffusion. Myoglobin‐loaded MAA hydrogels retained their heme reactivity after the immobilization process. The release of myoglobin incorporated by entrapment in MAA–PEGDMA hydrogels was highly influenced by the chain relaxation process. The diffusion coefficients of myoglobin incorporated by entrapment into anionic hydrogels were 2 orders of magnitude smaller (～ 10–13) than those for myoglobin incorporated by imbibition (10–11), both evaluated at pH 7.0. Substrate binding studies indicated that the protein biological activity was not compromised in those hydrogels loaded by the imbibition method, whereas prepolymeric solutions showed detrimental effects on protein stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Anionic ring‐opening polymerization of adipic anhydride initiated by potassium poly(ethylene glycol)ate

Poly(adipic anhydride) (PAA) was prepared by the ring‐opening polymerization of adipic anhydride (AA) initiated by potassium poly(ethylene glycol)ate. The effects of various factors, such as the amount of initiator, concentration of the monomer, reaction time and temperature, and polarity of the solvent on the polymerization were investigated. The crude polymerized product was a mixture of PAA homopolymer and poly(ethylene glycol)–poly(adipic anhydride) block copolymer, as confirmed by ¹H‐NMR and gel permeation chromatography. Chain‐transfer reactions occurred intensively for the AA polymerization in both the nonpolar solvent toluene and the polar solvents CHCl₃ and tetrahydrofuran, which predominantly determined the molecular weight and the monomer conversion for the polymerized product. The lower monomer conversion in toluene was ascribed to a lower livingness for the initiator in the nonpolar solvent when compared with other two, polar solvents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2194–2201, 2003     

Synthesis of end-branched poly(ethylene glycol)s by aqueous atom transfer radical polymerization

Summary This article reports the synthesis of novel hydrophilic end-branched poly(ethylene glycol)s, in aqueous media by atom transfer radical polymerization (ATRP). Poly(ethylene glycol)s with molecular weights 10,000 and 16,000 were end-functionalized and used as bifunctional initiators for the polymerization of a poly(ethylene glycol) macromonomer with a molecular weight of 2,000 (PEGMA), either by aqueous ATRP or in a watedmethanol (l/l V/V) mixture. For both macroinitiators a DP of 10 was the target, giving an average of 5 branches in each end. The rates of polymerization were of the same order of magnitude when the polymerizations were initiated by either of the two macroinitiators in watedmethanol (l/l V/V). When a bifunctional oligo(ethy1ene glycol) initiator (M_n = 600) was used to study the polymerization of PEGMA in water/methanol a reduction in the rate of polymerization was observed indicating an influence of the molecular weight of the initiator on the rate of polymerization. Received 25 Maich 2002/Revised 8 November 2002/Accepted 8 November 2002 Correspondence to Jorgen Kops     

Swelling characterization of poly (acrylamide-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="Italic">N</Emphasis>-vinylimidazole) hydrogels crosslinked by TMPTA and semi-IPN’s with PEG

In this study, a novel semi-interpenetrating network (semi-IPN’s) hydrogel, composed of acrylamide (AAm) with N-vinylimidazole (NVI) as comonomer, with poly (ethylene glycol)(PEG) and a multifunctional crosslinker such as trimethylolpropane triacrylate (TMPTA) was prepared. Highly swollen poly (AAm/NVI) hydrogels and semi-IPN’s were synthesized by free radical solution polymerization. Swelling experiments were performed in water at 25°C, gravimetrically. The influence of NVI and PEG content in hydrogels were examined. Poly (AAm/NVI) and poly (AAm/NVI/PEG) hydrogels showed large extents of swelling in aqueous media the swelling being highly dependent on the chemical composition of the hydrogels. Swelling ratio of poly (AAm/NVI) hydrogels and poly (AAm/NVI/PEG) hydrogels was shown 7.16–39.85. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non-Fickian in character. This study has given the quantitative information on the swelling characteristic of poly (AAm/NVI) hydrogel and semi-IPN’s as water absorbent in many potential applications.     

Novel thermosensitive hydrogel composites based on poly(d,l‐lactide‐co‐glycolide) nanoparticles embedded in poly(n‐isopropyl acrylamide) with sustained drug‐release behavior

To reach sustained drug release, a new composite drug‐delivery system consisting of poly(d,l ‐lactide‐co‐glycolide) (PLGA) nanoparticles (NPs) embedded in thermosensitive poly(N‐isopropyl acrylamide) (PNIPAAm) hydrogels was developed. The PNIPAAm hydrogels were synthesized by free‐radical polymerization and were crosslinked with poly(ethylene glycol) diacrylate, and the PLGA NPs were prepared by a water‐in‐oil‐in‐water double‐emulsion solvent‐evaporation method. The release behavior of the composite hydrogels loaded with albumin–fluorescein isothiocyanate conjugate was studied and compared with that of the drug‐loaded neat hydrogel and PLGA NPs. The results indicate that we could best control the release rate of the drug by loading it to the PLGA NPs and then embedding the whole system in the PNIPAAm hydrogels. The developed composite hydrogel systems showed near zero‐order drug‐release kinetics along with a reduction or omission of initial burst release. The differential scanning calorimetry results reveal that the lower critical solution temperature of the developed composite systems remained almost unchanged (<1°C increase only). Such a characteristic indicated that the thermosensitivity of the PNIPAAm hydrogel was not distinctively affected by the addition of PLGA NPs. In conclusion, an approach was demonstrated for the successful preparation of a new hybrid hydrogel system having improved drug‐release behavior with retained thermosensitivity. The developed systems have enormous potential for many biotechnological applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40625.