Formation Of Interpenetrating Polymer Networks Research Articles

Interpenetrating polymer network matrices of sodium alginate and carrageenan for controlled drug delivery application

Interpenetrating polymer network (IPN) matrices of sodium alginate and carrageenan were prepared for controlled release application. The propranolol-resin complex (resinate) loaded matrices were prepared by wet granulation/covalent crosslinking method and subsequently compressed into tablets. The SEM, DSC and XRD studies confirmed the amorphous nature of drug in the IPN matrix and FTIR confirmed the IPN formation and stability of drug within IPN matrix. The pure drug propranolol HCl showed rapid and complete dissolution within 60 min, while drug release from resinate was extended for 2.5 h and that from IPN tablets was still slower and drug release prolonged over 18 h. The crosslinking time of granules affected the release of drug from IPN matrix.

Effect of Interpenetrating Polymer Network Formation with Polystyrene on the Thermal Stability of Poly (2-hydroxyethyl methacrylate) and Poly (2-acetoxyethyl methacrylate)

Effect of Interpenetrating Polymer Network Formation with Polystyrene on the Thermal Stability of Poly (2-hydroxyethyl methacrylate) and Poly (2-acetoxyethyl methacrylate)

Morphology, mechanical and thermal properties of nano-structured full IPNs based on polyisoprene and PMMA

Morphology, mechanical properties, thermal stability and gas transport behaviour of interpenetrating polymer networks (IPNs) based on PI/PMMA have been investigated using various techniques. Crosslinking level of both phases and concentration of PMMA were found to have noticeable effects on the compatibility of immiscible components during IPN formation. Effect of crosslinking was studied by preparing IPNs with varying amount of crosslinker concentration in each phase. Crosslinking of both phases facilitated deeper interpenetrations between both networks, and certain degree of compatibility is attained during IPN formation. Nanometre-sized domains were observed for highly crosslinked IPN. Lower concentration of PMMA was found to favour phase mixing more effectively than others. DSC curve of 65/35 IPN showed a broad transition arising from the α and β-relaxations of PMMA due to the higher flexibility attained by mixing with the highly mobile PI chains. The mechanical properties of the IPNs were correlated to the morphology of the system and 50/50 composition showed maximum mechanical properties among the studied compositions. Mode of mechanical failure, thermal stability and gas transport behaviour were also analysed. IPNs having nanometre-sized domains showed least gas permeability among the studied samples.

Modification of poly(vinyl chloride) by IPN formation with poly(ethyl acrylate)

AbstractSemi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(ethyl acrylate) (PEA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PEA, respectively. These two types of IPNs have been compared with respect to their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi‐1 IPNs displayed a decrease in their tensile strength and modulus while in contrast; the semi‐2 IPNs exhibited a marginal increase with increasing crosslinked PEA incorporation. The semi‐1 and semi‐2 IPNs containing 10 and 30 wt % of PEA displayed a two‐stage degradation typical of PVC in their thermogravimetric and DSC studies while confirming the increased stability of the samples with higher percentages of PEA. The softening characteristics as detected by the extent of penetration of the thermomechanical probe as has been detected by thermomechanical analysis are in conformity with their mechanicals. The biphasic cocontinuous systems as explicit from the morphological studies reveal fibrillar characteristics in both the systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Visualizing phase separation in polystyrene/polystyrene homo‐IPNs via sulfonation

AbstractBACKGROUND: Polystyrene/polystyrene (PS/PS) interpenetrating polymer networks (IPNs) represent ideal homo‐IPNs. Whether phase separation occurs in this system has been a long‐standing problem, which is closely related to the self‐organization mechanism in IPN formation and is important to the exploration of new polymer morphologies and properties by topological isomerism.RESULTS: A series of bead samples of PS/PS sequential IPNs with the same nominal divinylbenzene contents were synthesized by suspension polymerization, followed by sulfonation. Scanning electron micrographs and energy‐dispersive X‐ray mapping show unique distinctive topography on both surfaces and fractured surfaces and large heterogeneity in sulfonation of the PS/PS IPN beads, which for the first time provide visual evidence for dual‐phase continuity in PS/PS IPNs.CONCLUSION: The phase separation behavior is proposed to be due to hydrodynamic screening, architectural asymmetry and excluded volume interactions between network I and the precursor chains of network II. This is considered to represent pure IPN effects in sequential formation and may shed light on the general constitution mechanism and molecular design of IPN materials. Copyright © 2009 Society of Chemical Industry

STUDIES ON APPARENT KINETICS AND RHEOLOGICAL BEHAVIOR OF EPOXY/ACRYLATE IPNS AS VACUUM PRESSURE IMPREGNATION RESINS

The apparent kinetics and cure behavior of novel interpenetrating polymer networks (IPNs) based on cycloaliphatic epoxy resin (CER) and tri-functional acrylate have been investigated by means of differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The results of DSC measurements show that the curing reaction of the TMPTMA component is much earlier than that of the CER component, which can lead to the formation of the IPNs. In contrast to neat anhydride-CER system, the anhydride-CER/TMPTMA systems exhibit relatively lower curing temperatures. The activation energy for initiating the reaction of the anhydride-CER system slightly increases, whereas the activation energy for propagating the reaction markedly reduces during the full IPNs formation. The FT-IR spectroscopic changes are interpreted in terms of curing mechanism of CER and TMPTMA components. The extent of reaction is calculated from FT-IR absorption bands, which depends on the reactive group concentration. The experimental results of FT-IR measurements are in good agreements with those of DSC measurements. The rheological behavior of anhydride-CER/TMPTMA systems during IPNs formation is studied in this paper. It is confirmed that the introduction of TMPTMA monomer into anhydride-epoxy resin has significant effects on the rheological behavior of the system.

Synthesis and characterization of biodegradable interpenetrating polymer networks based on gelatin and divinyl ester synthesized from poly(caprolactone diol)

AbstractThis article describes the synthesis and characterization of interpenetrating polymer networks (IPNs) from hydrophilic and hydrophobic polymers using emulsification technique. Tween 20 (0.001 wt % of gelatin) was employed as emulsifier for the preparation of semi and full IPNs. Gelatin (G), a hydrophilic component was crosslinked by glutaraldehyde (Glu) and divinyl ester (DVE), a hydrophobic component was polymerized/crosslinked using 3 mol % of AIBN as an initiator. Structural characterization was done using FTIR (doublet at 1620 and 1636 cm−1) and NMR (signals in the range of δ = 5–7 ppm), which confirmed the formation of DVE. Several samples were prepared by varying the ratio of gelatin : DVE (w/w) and the Glu concentration. The swelling characteristics (as a function of varying pH maintained using buffers) and degradation behavior (in phosphate buffer saline pH 7.4) of hydrogels was studied to investigate the effect of composition and crosslinker concentration. Percent water uptake decreased from 496 to 181 at pH 7.4 and pH 6.5 in IPNs as the concentration of DVE increased from 0.3 g to 0.7 g per g of gelatin. Semi‐IPNs, where DVE was not polymerized, demonstrated higher swelling at pH 7.4 in contrast to pH 6.5 irrespective of Glu concentration. Gelatin hydrogels degraded within 180 h and IPNs degraded within 290 h whereas DVE did not degrade till the study period of 20 days. The formation of IPN was confirmed by thermal characterization (DSC, TGA) and scanning electron microscopy (SEM). Observation of cross‐sectional microstructure of disrupted honeycomb of Gx into closely packed fiber‐like structure upon interpenetration by SEM clearly suggests the formation of IPN. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

On-line monitoring of cycloaliphatic epoxy/acrylate interpenetrating polymer networks formation and characterization of their mechanical properties

The novel interpenetrating polymer networks (IPNs) based on cycloaliphatic epoxy resin (CER) containing cyclohexene oxide groups and tri-functional acrylate, trimethylol-1, 1, 1-propane trimethacrylate (TMPTMA) were synthesized. The formation of the IPNs was on-line monitored by means of polarizing optical microscope, time-resolved light scattering and Fourier transform infrared spectroscopy. The morphological and mechanical properties of the resultant IPNs were investigated and evaluated with scanning electron microscopy (SEM) and dynamical thermal mechanical analysis (DTMA), respectively. The on-line monitoring results showed that during the course of the IPNs formation, the TMPTMA component was cured more quickly than the CER component, leading to the formation of the sequential IPNs. During the early curing stage, there were the phase separation phenomena in the CER/TMPTMA system. The SEM results revealed that although there were some slight phase separation phenomena in the CER/TMPTMA system in the early curing stage, the resultant IPNs displayed the homogeneous structures and did not show the apparent phase separation morphology. The DTMA results revealed that the resulting IPNs exhibited rather higher modulus and denser cross-linking network structure than the neat CER system.

Hydrogel-elastomer composite biomaterials: 3. Effects of gelatin molecular weight and type on the preparation and physical properties of interpenetrating polymer networks

To optimize the preparation of a gelatin-HydroThane Interpenetrating Polymer Network (IPN) and obtain optimum physical properties for its use as a wound dressing, we studied IPN films prepared with two types of gelatin having different molecular weights. The effects of the gelatin molecular weight and type on the IPN film's structure, morphology, swelling and mechanical properties were determined. While FTIR did not reveal any noticeable differences between the IPNs prepared using different gelatin, light microscopy showed a lesser phase separation of the film prepared with a high-molecular-weight type A gelatin. Furthermore, these films displayed slightly less swelling, higher strength and lower strain, compared to the IPNs prepared with either low-molecular-weight type A or type B gelatin. The IPN prepared with type B gelatin showed higher swelling in serum-containing medium than those prepared with type A gelatin, because of its ionic charges under the condition. Increases in viscosity were observed with increasing molecular weight, type A being more viscous than type B gelatin despite having a lower bloom number. The viscosity of the high-molecular-weight gelatin was in the same magnitude as that of HydroThane, which might lead to less phase separation. A better understanding of the effects of alterations in the gelatin molecular weight and type on the formation and properties of the gelatin-HydroThane IPN should facilitate the development of promising composite biomaterials for wound dressing applications.

Combinatorial Methods and Informatics Provide Insight into Physical Properties and Structure Relationships during IPN Formation

AbstractCombinatorial methods and informatics are applied to the study of complex property‐structure‐processing relationships during interpenetrating polymer network formation in an epoxy/acrylate system. Principal component analysis of a dataset that covers different compositions and process sequences successfully identifies the most unique samples as well as relationships between material properties. The relationships between material properties can be exploited in future investigations by allowing high throughput screening and as a guide for engineering materials. The use of combinatorial methods, high throughput screening, and informatics will lead to accelerated material design.magnified image

Hydrogel-elastomer composite biomaterials: 2. Effects of aging methacrylated gelatin solutions on the preparation and physical properties of interpenetrating polymer networks

This study was conducted to understand the effects of aging methacrylated gelatin solutions on the properties of gelatin-HydroThane Interpenetrating Polymer Network (IPN) films. The latter were prepared from methacrylated gelatin solutions that were either freshly made or stored at different concentrations and temperatures for various periods. The morphology, swelling stability and mechanical properties of the IPNs were then accordingly characterized. The IPNs prepared with aged solutions showed a reduced phase separation; changed from a network-like structure to a continuous phase structure; and demonstrated higher swelling stabilities and higher elasticity under optimal aging conditions, compared to the IPN prepared with a fresh methacrylated gelatin solution. An increase in viscosity and a change in phase transition of aged methacrylated gelatin solutions were also observed, presumably due to the physical structuring of methacrylated gelatin chains (e.g., by the formation of a helix structure), thus altering the resulting IPN characteristics. A better understanding of the effects of aging methacrylated gelatin solution on the formation and properties of gelatin-HydroThane IPNs should enable us to further develop our composite biomaterials for different dressing applications.

Development of Biocompatible Interpenetrating Polymer Networks Containing a Sulfobetaine-Based Polymer and a Segmented Polyurethane for Protein Resistance

Interpenetrating polymer networks (IPNs) were prepared by the modification of a segmented polyurethane (SPU) with a cross-linked sulfobetaine methacrylate (SBMA) polymer. The IPN films that were prepared can effectively resist nonspecific protein adsorption when the distribution of SBMA units within the SPU film is well controlled, and they retain high mechanical strengths inherent from the base SPU films. Furthermore, the zwitterionic and biomimetic nature of sulfobetaine and the ease of SBMA preparation make SBMA-based materials very attractive for a wide range of applications. It is challenging to control the diffusion of highly polar SBMA into the hydrophobic network of SPU. In this study, various parameters governing the formation of IPNs containing SBMA were studied. The chemical composition depth profile of the IPN films was determined by confocal Raman microscopy. The morphology and thickness of these IPN films were examined by atomic force microscopy and scanning electron microscopy. The amount of adsorbed proteins on the IPN films was determined by an enzyme-linked immunosorbent assay. Results show that the amount of adsorbed proteins on the IPN films depends on the incubation conditions, including solvent polarity, incubation time, SBMA monomer ratio, and incubation concentration. It appears that the IPN films prepared in a mixed solvent of higher polarity with long incubation time lead to very low protein adsorption. This study not only introduces a new IPN system containing SBMA, but also provides a fundamental understanding of various parameters governing the formation of IPNs.

Sequential interpenetrating polymer network based on styrene butadiene rubber and polyalkyl methacrylates

AbstractA series of sequential interpenetrating polymer network (IPNs) based on styrene butadiene rubber (SBR) and polyalkyl (methyl, ethyl, and butyl) methacrylates have been prepared by using tetraethylene glycol dimethacrylate as crosslinker. The IPNs were characterized by infrared spectrophotometer, dynamic mechanical analyzer, thermogravimetric analyzer, and swelling study. IPNs have exhibited higher tensile properties compared with pure SBR. IPNs based on PMMA have shown higher tensile strength compared with others. Dynamic mechanical analysis has shown that the IPNs have superior dynamic properties than SBR. Because of IPN formation, tan δ peak shifted inward between SBR and acrylates. Although the magnitude of tan δ decreased, the peaks were broadened because of micro heterogeneous phase separation. At higher concentration of methacrylate, splitting in tan δ peak was noticed because of phase separation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1120–1126, 2007

The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy‐acrylate system

The kinetics of thermally initiated cationic epoxy polymerization and free radical acrylate photopolymerization were studied using photo-differential scanning calorimetry. The reactions of the neat monomers and diluted monomers as well as interpenetrating polymer networks (IPNs) were studied as a function of dilution by the other monomer and temperature. The reaction sequence was also varied to study its effect on the kinetics of formation of the simultaneous IPN's. Both reactions quickly become diffusion controlled. The effects of increasing temperature and dilution on the acrylate polymerization rate profiles are similar, leading to reduced polymerization rate and longer polymerization times. The dilution effect on the epoxy polymerization is similar to that of the acrylate. However, unlike the acrylate reaction the epoxy polymerization rate increases strongly with temperature. The preexistence of one polymer has a significant effect on the polymerization of the second monomer. This effect is larger for the acrylate than for the epoxy polymerization. New kinetic models are needed to capture these complex behaviors.

Polyisobutene–poly(methylmethacrylate) interpenetrating polymer networks: synthesis and characterization

Interpenetrating polymer networks (IPNs) combining polyisobutene (PIB) and poly(methyl methacrylate) (PMMA) networks were prepared using a in situ strategy. PIB networks were formed by isocyanate—alcohol addition between the hydroxyl end groups of telechelic dihydroxy-polyisobutene and an isocyanate cross-linker, catalyzed by dibutyltindilaurate (DBTDL). PMMA networks were obtained from free-radical co-polymerization of methyl methacrylate (MMA) with ethylene glycol bismethacrylate (EGDM) in the presence of dicyclohexyl peroxydicarbonate (DCPD) as the initiator. The synthesis of each network during the IPN formation was followed by FTIR spectroscopy. The highest degree of interpenetration is obtained by forming the PIB network first. The corresponding transparent IPNs exhibit two mechanical relaxation temperatures as determined by Dynamic mechanical thermal analysis (DMTA), corresponding to those of PMMA and PIB enriched phases. Mechanical properties of PIB networks are tremendously improved by the presence of PMMA network in such IPN architecture.

Sequential interpenetrating polymer network of poly(ethyl methacrylate) and carboxylated nitrile rubber: Dynamic mechanical analysis and morphology

AbstractAn interpenetrating polymer network (IPN) based on poly(ethyl methacrylate) (PEMA) and carboxylated nitrile rubber was synthesized. Peroxide crosslinked XNBR was swollen in ethyl methacrylate containing benzoyl peroxide as initiator and tetraethylene glycol dimethacrylate as crosslinking agent. A full and sequential IPN is formed by the two independently crosslinked phases of XNBR and PEMA. Dynamic mechanical analysis of the 50/50 XNBR/PEMA IPN shows a single, broad peak whereas a 50/50 blend shows two distinct peaks, indicating the pinning down of a microheterogeneous structure during the IPN formation rather that macrophase separation as in blends. SEM analysis confirms the development of a cocontinuous intimate structure of the IPN. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1487–1491, 2005

Synthesis and swelling behaviour of interpenetrating network polymers of poly(vinyl alcohol) and poly(acrylamide-co-potassium methacrylate)

A series of interpenetrating polymer networks (IPN) based on poly(vinyl alcohol) and poly(acrylamide-co-potassium methacrylate) were synthesized. The synthesis was effected by a semi-IPN method polymerizing an aqueous solution of acrylamide and potassium methacrylate using the APS/TMEDA initiating system with a cross-linker, in the presence of poly(vinyl alcohol). Four different cross-linkers were employed in the preparation of IPNs. The swelling behaviour of the IPNs was monitored as a function of acrylamide and potassium methacrylate ratios. The IPNs were synthesized by varying the cross-linker concentration and the experimental results showed that the cross-linker concentration is of great influence on the swelling behaviour. The network formation of IPNs cross-linked with various cross-linkers at two different concentrations was studied in detail by scanning electron microscopy (SEM). The IPNs being ionic, swelling is affected by the ionic strength as well as by the pH of the medium. Further the effect of simulated biological fluids on the swelling behaviour of PVA/poly(AAm-co-KMA) IPNs was also investigated.

Physicochemical characterisation and biological evaluation of hydrogel-poly(ε-caprolactone) interpenetrating polymer networks as novel urinary biomaterials

Hydrogels are frequently employed as medical device biomaterials due to their advantageous biological properties, e.g. resistance to infection and encrustation, biocompatibility; however, their poor mechanical properties generally limit the scope of application to coatings of medical devices. To address this limitation, this study described the formulation of sequential interpenetrating polymer networks (IPN) of poly(ε-caprolactone) (PCL) and poly(hydroxyethylmethacrylate) (p(HEMA)). IPN containing 20% w/w PCL, p(HEMA), both in the presence or absence of ethyleneglycol dimethacrylate (EGDMA 1% w/w), were prepared by free radical polymerisation. Following preparation the degradation and the mechanical and surface properties of the biomaterials and, in addition, the resistances to microbial adherence and encrustation in vitro were examined. In comparison to p(HEMA) the various IPN exhibited substantially greater tensile properties (ultimate tensile strength, % elongation, Young's modulus) that were accredited to the discrete distribution of PCL within the hydrogel network. The IPN exhibited two glass transition temperatures that were statistically similar to those of the individual components, thereby providing evidence of the immiscible nature of the two polymers. The IPN possessed higher receding contact angles and lower equilibrium water contents in comparison to p(HEMA), whereas the limited degradation of the IPN at both pH 7 and 9 was deemed suitable for clinical usage for periods of at least 4 weeks. The resistances of the various IPN to bacterial adherence and urinary encrustation were examined using in vitro models. Importantly the resistance of the IPN to encrustation was, in general, similar to that of p(HEMA) but greater than that of PCL whereas, the resistance of the IPN to bacterial adherence was frequently greater than that of p(HEMA) and PCL. Therefore, this study has shown that the mechanical properties of p(HEMA) may be substantially increased by the formation of IPN with PCL whilst maintaining other appropriate physicochemical properties and resistances to urinary encrustation and bacterial adherence. It is suggested that these IPN may be suitable for device fabrication thereby expanding the manufacturing application of hydrogels without compromising their potential clinical efficacy.

Engineering properties of Novolac resin‐PMMA{poly(methyl methacrylate)} IPN system

AbstractFull and semi interpenetrating polymer networks (IPNs) based on phenol‐formaldehyde resin (Novolac) and poly(methyl methacrylate) have been made by in situ sequential technique of IPN formation. These systems of different compositions were characterized with respect to their mechanical properties, such as, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Extent of phase mixing of the two polymers was envisaged from the micrographs obtained by polarizing light microscopy (PLM). The effects of variation of the blend ratios on the above‐mentioned properties were examined. There was a decreasing trend of modulus and UTS with consequent increases in elongation at break and toughness for both types of IPNs with increase in proportions of PMMA. Lowering of glass transition temperatures (with respect to pure crosslinked Novolac resin) of the IPNs with increasing proportions of PMMA was observed, indicating a plasticizing influence of PMMA on the rigid and brittle matrix of phenolic resin. The TGA thermograms exhibit lowering in thermal stability of the IPNs with respect to pure phenolic resin in the regions of higher temperatures. With increase in proportion of PMMA the onset of degradation of the IPNs is shifted towards lower temperature zone. The surface morphology as revealed by PLM indicates distribution of discrete domains of PMMA in the phenolic resin matrix. The two phase interfaces are quite sharp at higher concentrations of PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2764–2774, 2004

Crosslinking polymerization leading to interpenetrating polymer network formation. 3. Polyaddition crosslinking reaction of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with poly(oxytetramethylene) glycol in the presence of linear polymethacrylate resulting in semi-interpenetrating polymer network

As part of a series of our works concerned with the elucidation of the crosslinking polymerization mechanism leading to the interpenetrating polymer network (IPN) formation, in which IPN consists of both polyurethane (PU) and polymethacrylate (PM) networks, this article deals with the polyaddition crosslinking reactions of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) poly(MMA-co-MOI) [MMA/MOI = 99/1] as a novel multifunctional polyisocyanate with poly(oxytetramethylene) glycol [H-(OCH2CH2CH2CH2)n-OH (n = 28)] (POTMG-28) in the presence of two types of linear PMs, differently miscible with the resulting PU networks, leading to semi-IPN formation. Thus, poly(MMA-co-MOI) was prepared by the radical copolymerization of MOI with MMA in the presence of CBr4 as a chain-transfer agent. No influence of the linear PM on the rate of polyaddition crosslinking reaction was observed. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation: the deviation of the actual gel point from the theoretical one was rather small, close to the ideality, and the delayed gelation from theory tended to become a little smaller in the presence of PM. These are discussed mechanistically to deepen the understanding of the PU network formation in the presence of a linear PM resulting in semi-IPN, along with the data of the intrinsic viscosities of resulting prepolymers. To collect a direct evidence of semi-IPN formation, we attempted to pursue the incorporation of the linear PM into the resulting PU networks by 1H-NMR and UV-vis spectroscopy; in the latter case, the copolymers containing a small amount of pyrenyl methacrylate were used as linear PMs because the pyrenyl group was employed as the probe for UV-vis spectroscopic determination of the amount of the incorporated PM. The swelling ratio of the gel became lower in the presence of a linear PM. All data for the polyaddition crosslinking reactions of poly(MMA-co-MOI) with POTMG-28 in the presence of PM, along with the mechanistic discussion, demonstrate that the freely compatible molecular interaction would lead to a true semi-IPN formation as a result of the good miscibility between PU networks and a linear PM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1198–1208, 2004