A novel pH‐sensitive gelatin–DNA semi‐interpenetrating polymer network hydrogel

Gelatin and DNA were mixed together in various ratios followed by the addition of glutaraldehyde as a cross‐linker. FT‐IR spectroscopy confirmed the formation of a semi‐interpenetrating polymer network (semi‐IPN) between the gelatin and DNA. The gelatin–DNA semi‐IPN hydrogel underwent, reversibly, remarkable changes in swelling degree in response to the variation of pH. In the low‐pH range, the hydrogel showed a lower swelling degree; with an increment in pH, the hydrogel was highly swollen, which is considered to originate from the complexation and de‐complexation between gelatin and DNA, as was verified by turbidity measurements. Higher contents of DNA result in an increase in the swelling degree, which is presumably due to the easy outward expansion of free DNA moieties. The permeability coefficient, P, for a model molecule, cimetidine, through the semi‐IPN hydrogel membranes was determined in pH 1.0 and pH 12.0 buffer solutions. The results show that the permeation of cimetidine is responsive to pH change, and an evident variation in the P values occurs in response to the pH of the media. Copyright © 2004 Society of Chemical Industry     

Polymer–protein interaction,water retention,and biocompatibility of a stimuli‐sensitive superporous hydrogel containing interpenetrating polymer networks

The swelling of a superporous hydrogel containing poly(acrylic acid‐co‐acrylamide)/O‐carboxymethyl chitosan interpenetrating polymer networks (SPH‐IPN) was sensitive toward the pH, ionic strength, and temperature stimuli. With insulin as a model drug, polymer–protein interaction was detected, and it was physical rather than covalent. Freezing water was the majority of the imbibed water in the swollen SPH‐IPNs, and the water‐retention ability of the polymer against compression and time of exposure at 37°C was improved as the amount of the O‐carboxymethyl chitosan network increased. A 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) assay on AD293 and RBL‐2H3 cells and an in situ lactate dehydrogenase assay and morphological study on rat intestine confirmed that the SPH‐IPNs had satisfactory biocompatibility. These pronounced properties suggested that the SPH‐IPNs could be developed as an attractive peroral delivery vehicle for peptide and protein drugs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide)

In this study, pH‐ and temperature‐responsive hydrogels based on linear sodium alginate (SA) and crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by semi‐interpenetrating network (semi‐IPN) technique. The dually responsive hydrogels were characterized by FTIR, DSC, and SEM, and their temperature‐ and pH‐responsive behaviors were investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these hydrogels underwent volume phase transition at around 33°C irrespective of the pH value of the medium, but their pH sensitivity was evident only below their volume phase transition temperature. Under basic conditions, the swelling ratios of SA/PNIPAAm semi‐IPN hydrogels were greater than that of pure PNIPAAm hydrogel and increased with increasing SA content incorporated into the hydrogels, but the case was inverse under acidic conditions. The pulsatile swelling experiments indicated that the higher the SA content in SA/PNIPAAm semi‐IPN hydrogels, the faster the response rate to both pH and temperature change. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1931–1940, 2005     

Synthesis and mechanical properties of leather–epoxy interpenetrating polymer networks

Leather–epoxy interpenetrating polymer networks (IPNs) were synthesized; these IPNs have an approximate epoxy concentration of 25 wt %. The flexural and tensile moduli of the IPNs prepared are equivalent to those of the epoxy resin. The Izod impact energy and fracture toughness measured for the IPNs, however, exceed those attained by the epoxy resin alone by at least a factor of 4. The glass transition of leather–epoxy IPNs occurs over a wide temperature range, thus indicating that the IPN is an intimate admixture of the epoxy resin throughout the collagen matrix of the hide. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1224–1232, 2000     

Synthesis and characteristics of interpenetrating polymer network hydrogel composed of chitosan and poly(acrylic acid)

Interpenetrating polymer network (IPN) hydrogels composed of chitosan and poly(acrylic acid) (PAAc) were synthesized by UV irradiation method, and their structure, crystallinity, swelling behavior, thermal property, and mechanical property were investigated. Chitosan/PAAc IPNs exhibited relatively high equilibrium water content and also showed reasonable sensitivity to pH. From the swelling behaviors at various pH's, Fourier transform infrared spectra at high temperature and thermal analysis confirmed the formation of polyelectrolyte complex due to the reaction between amino groups in chitosan and carboxyl groups in PAAc. For this reason, even at a swollen state, the present chitosan/PAAc IPNs possess good mechanical properties. Particularly, the CA‐2 sample (with a weight ratio of chitosan/PAAc = 50/50, molar ratio [NH₂]/[COOH] = 25/75) showed the lowest equilibrium water content and free water content, attributed to the more compact structure of the polyelectrolyte than CA‐1 or CA‐3 due to the high amount of interchain bond within the IPN. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 113–120, 1999     

Synthesis and properties of the semi‐interpenetrating polymer network–like,thermosensitive poly(N‐isopropylacrylamide) hydrogel

A new strategy was used to prepare a semi‐interpenetrating polymer network (semi‐IPN)–like poly(N‐isopropylacrylamide) (PNIPAAm) polymeric hydrogel, consisting of either low (2300) or high (33,000) molecular weight linear PNIPAAm chains and the crosslinked PNIPAAm network. The properties of the resulting PNIPAAm hydrogels were characterized by DSC and SEM as well as their swelling ratios at various temperatures, the deswelling in hot water (48°C), and the oscillating shrinking–swelling properties within small temperature cycles. It was found that the deswelling rate of these semi‐IPN–like PNIPAAm hydrogels was improved if the molecular weight and/or composition of the linear PNIPAAm chains within the semi‐IPN–like PNIPAAm hydrogels were increased. This improved deswelling rate was attributed to the fast response nature of the linear PNIPAAm chains and the increased pore number in the matrix network, which provided numerous water channels for the water to diffuse out during the deswelling process at a temperature above the lower critical solution temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1935–1941, 2003     

Synthesis and characterization of pH‐ and temperature‐sensitive silk sericin/poly(N‐isopropylacrylamide) interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of silk sericin (SS) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared simultaneously. The properties of the resultant IPN hydrogels were characterized by differential scanning calorimetry and SEM as well as their swelling behavior at various temperatures and pH values. The single glass transition temperature (T_g) presented in the IPN thermograms indicated that SS and PNIPAAm form a miscible pair. The swollen morphology of the IPNs observed by SEM demonstrated that water channels (pores present in SEM micrographs) were distributed homogeneously through out the network membranes. The swelling ratio of the IPNs depended significantly on the composition, temperature and pH of the buffer solutions. The dynamic transport of water into the IPN membrane was analyzed based on the Fickian equation. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of fluorinated polyacrylate–cellulose acetate butyrate interpenetrating polymer networks

Fluorinated polyacrylates are highly hydrophobic and oleophobic. However, their poor mechanical properties prevent their development in many applications. Combination of a fluorinated polyacrylate network with a rigid cellulose acetate butyrate (CAB) network in an interpenetrating polymer network (IPN) architecture is an effective method for improving the mechanical properties of fluorinated polyacrylates. IPNs combining poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate) (polyAcRf6) with CAB were prepared according to an in situ polymerization/crosslinking synthesis. CAB was crosslinked by addition between unmodified hydroxyl groups and the isocyanate of a pluri‐isocyanate crosslinker. The fluorinated network was obtained through free‐radical copolymerization of 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate with poly(ethylene glycol dimethacrylate). The rates of formation of both networks were followed using Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) of IPNs show a single glass transition temperature and a single mechanical relaxation temperature, which are characteristic of a high degree of interpenetration between the partner networks. The mechanical properties of IPNs are greatly improved compared with those of the single fluorinated network. CAB/polyAcRf6 IPNs were prepared, and characterized using DSC and DMTA as well as contact angle measurements for their surface properties. As hoped, the mechanical properties of such materials are much improved compared with those of the fluorinated partner alone. Copyright © 2010 Society of Chemical Industry     

Epoxy resin–poly(ethyl methacrylate) interpenetrating polymer networks: Morphology,mechanical, and thermal properties

Full (interpenetrating networks (IPNs)) and semi-IPNs of the epoxy resin and poly(ethyl methacrylate) (PEMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, namely, tensile strength, elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry and thermogravimetry. The morphological features were studied through scanning electron microscopy (SEM) and polarized light microscopy. The effects of variation of the blend ratios on the above-mentioned properties were examined. There was a gradual decrease of modulus and tensile strength with consequent increases in elongation at break and toughness for both types of IPNs with increases in PEMA content. The weight retentions in the thermal decomposition of both the semi-IPNs and full IPNs were higher than the epoxy homopolymer. This enhancement was presumably related to the presence of the unzipped ethyl methacrylate monomer, which acted as radical scavengers in the epoxy degradation. An inward shift and lowering (with respect to pure epoxy) of the T_g of the IPNs was observed. The polarized light microscopy exhibits bimodal distribution of particle sizes. The fractography as studied by SEM shows change in fracture mechanics from shear yielding to crazing with increasing PEMA content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1051–1059, 1998     

Polyurethane–epoxy maleate of bisphenol a semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks were synthesized starting from polyurethane (PU) and epoxy maleate of bisphenol A (EMBA). Differential scanning calorimetry and swelling measurements showed good miscibility and the presence of the strong intermolecular interactions within the synthesized networks. The physicomechanical properties increased against PU to a maximum value with the increasing of EMBA content up to 12 wt % and then decreased with further increasing EMBA content. Generally, with exception of the elongation at the limit of elasticity, the mechanical properties improved very much under action of the UV radiation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 138–144, 2002     

EA/St-AN互穿聚合物网络的加工和力学性能

以丙烯酸乙酯为软单体 ,苯乙烯和丙烯腈为硬单体 ,二乙烯基苯或三乙二醇双丙烯酸酯为交联剂 ,采用多步种子乳液聚合技术制备了半互穿和全互穿聚合物网络 ,研究了软、硬单体配比 ,交联剂用量 ,加工次数对共聚物流变行为、力学性能和结构形态的影响。结果表明 ,制备的半互穿和全互穿聚合物网络均可在适宜的条件下流动成型。如果配方选择适当 ,反复加工后力学性能基本不变     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

Synthesis and characteristics of the interpenetrating polymer network hydrogel composed of chitosan and polyallylamine

A temperature‐ and pH‐dependent hydrogel was studied with interpenetrating polymer network (IPN) hydrogels constructed with water‐insoluble chitosan and polyallylamine. Various IPNs were prepared from different weight ratios of chitosan–polyallylamine. Crosslinked‐IPN hydrogels exhibited relatively high equilibrium water content (EWC) in the range 80–83%. The EWC of IPN hydrogels depended on pH and the amount of complex, which is the content of chitosan and polyallylamine. The differential scanning calorimeter (DSC) thermogram of fully swollen IPN hydrogels appeared between 3 to 4 °C. The IPNs exhibited two glass‐transition temperatures (T_gs), indicating the presence of phase separation in the IPNs as exhibited by dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 498–503, 2002     

Swelling and drug‐release behavior of the poly(AA‐co‐N‐vinyl pyrrolidone)/chitosan interpenetrating polymer network hydrogels

A series of novel hydrogels were prepared from acrylic acid (AA), N‐vinyl pyrrolidone (NVP), and chitosan by photopolymerization. The swelling behavior, gel strength, and drug release behavior of the poly(AA/NVP) copolymeric hydrogels and corresponding interpenetrating polymer network hydrogels were investigated. Results showed that the swelling ratios for the present hydrogels decreased with an increase of NVP content in the gel, but the gel strength increased with an increase of NVP content in the gel. Results also showed that the drug‐release behavior for the gels is related to the ionicity of drug and the swelling ratio of the gel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2135–2142, 2004     

Silicone‐based hydrogels prepared by interpenetrating polymer network synthesis: Swelling properties and confinements effects on the formation kinetics

In this work, interpenetrating polymer networks (IPNs) of polydimethylsiloxane (PDMS) and poly(acrylic acid) or poly(2‐hydroxyethyl methacrylate) (PHEMA) have been synthesized employing a sequential method. Monomeric AAc or HEMA was introduced into the PDMS network by swelling the polymer in solutions of monomer. The polymerization of monomers was then conducted in the swollen network. The swelling properties of the IPNs were investigated by varying the monomer concentrations in the polymerization and more swelling was observed with low monomer concentrations due to the prevalence of cyclization reactions. Multi‐step polymerization used to achieve IPNs with high hydrogel contents, did not improve their water uptake. The kinetics of acrylic acid polymerization was studied under various conditions. Specifically, in the presence of confinement effects imposed by the PDMS network a considerable drop in the rate of reaction was observed. The cross‐linking density of the PDMS network was also studied how to affect the reaction rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and application of semi‐interpenetrating liquid crystalline polymer networks LCP/PS

Attempts to extend the IPN technology to liquid crystalline polymer (LCP) systems have been made in search for a new approach for enhancing the compatibility of liquid crystalline polymer with engineering thermoplastics. A new type of interpenetrating polymer network based on liquid crystalline polymer : semi‐interpenetrating liquid crystalline polymer network comprising liquid crystalline polymer PET/60PHB (LCP) and crosslinked polystyrene (PS) (for short: semi‐ILCPN LCP/PS) has been successfully prepared. The compatibility and thermal properties of the semi‐ILCPN LCP/PS with different amount of crosslinking agent were investigated by FTIR, SEM, DSC, and TGA, respectively. Furthermore, the possible application of the semi‐ILCPN LCP/PS as a new kind of compatibilizer in PPO/LCP blends was also studied and discussed. Well‐compatibilized PPO/LCP composites with considerably improved mechanical properties were obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1141–1150, 2000     

Swelling behavior and biocompatibility of Carbopol‐containing superporous hydrogel composites

Carbopol‐containing superporous hydrogel composites (SPHCc) with fast swelling and high swelling ratio were prepared using free radical copolymerization. Swelling behavior of the SPHCc was studied in various salt and pH solutions and their biocompatibility was evaluated using tissue damage and cytotoxicity studies. The swelling ratio of the SPHCc decreased with the increase of Carbopol/monomer ratio and was sensitive to pH and ionic strength of the swelling medium. The release of insulin from the SPHCc was rapid in 0.01M phosphate buffered saline (PBS, pH 7.4). In the jejunum mucosal membrane toxicity studies in rat, no significant morphological damage was observed after application of SPHCc. Besides, no damage of the Caco‐2 monolayers was detected after incubation with SPHCc in the trypan blue and propidium iodide tests. On the basis of these results, it was concluded that the SPHCc might be a safe and effective carrier for peroral delivery of peptide and protein drugs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

丙烯酸酯系胶乳互穿聚合物网络的合成及阻尼性能

以种子乳液聚合法合成了聚苯乙烯／聚丙烯酸乙酯、聚甲基丙烯酸乙酯／聚丙烯酸丁酯的核-壳胶乳互穿聚合物网络(LIPN),分别测试了不同配比LIPN及其共混物的阻尼性能、物理机械性能和吸水性能。结果表明,LIPN共混物是具有阻尼温域宽、阻尼性能优、物理机械性能良好和吸水率较低的阻尼材料,其阻尼性能主要取决于共混组分的性能、配比和内耗能的贡献,并且与共混物的织态结构也密切相关。     

Preparation and antidehydration of interpenetrating polymer network hydrogels based on 2‐hydroxyethyl methacrylate and N‐vinyl‐2‐pyrrolidone

This work reports the preparation of 2‐hydroxyethyl methacrylate (HEMA)/N‐vinyl‐2‐pyrrolidone (NVP) interpenetrating polymer network (IPN) hydrogels by UV‐initiated polymerization in the presence of free radical photoinitiator Darocur 1173 and cationic photoinitiator 4,4′‐dimethyl diphenyl iodonium hexafluorophosphate. The polymerization mechanism was investigated by the formation of gel network. The structure and morphology of the HEMA/NVP IPN hydrogels were characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). The results showed that the IPN gels exhibited homogeneous morphology. The dehydration rates of HEMA/NVP IPN hydrogels were examined by the gravimetric method. The results revealed that the hydrogels had a significant improvement of antidehydration ability in comparison with poly(2‐hydroxyethyl methacrylate)(PHEMA) hydrogel embedded physically with poly(N‐vinyl‐2‐pyrrolidone)(PVP). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,thermal properties,and morphology of blocked polyurethane/epoxy full‐interpenetrating polymer network

Blocked polyurethane (PU)/epoxy full‐interpenetrating polymer network (full‐IPN) were synthesized from blocked NCO‐terminated PU prepolymer, with 4,4‐methylene diamine as a chain extender and epoxy prepolymer, with 4,4‐methylene diamine as a curing agent, using simultaneous polymerization (SIN) method. From FTIR spectra analysis it was found that the major reactions in the blocked PU/epoxy IPN system are the self‐polymerization of block PU/chain extender and the self‐polymerization of epoxy/curing agent. Meanwhile, from reaction mechanisms the copolymerization of IPN may have occurred at the same time. The weight loss by thermogravimetric analysis decreased with increasing epoxy and filler content. It was confirmed from scanning electron micrography (SEM) that when the blocked PU content increased, the microstructure of IPN became rougher. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 323–328, 2006