Vernonia oil–based acrylate and methacrylate polymers and interpenetrating polymer networks with epoxy resins

Acrylate and methacrylate monomers were obtained by reacting vernonia oil, a naturally epoxidized oil, with acrylic or methacrylic acid. The highest conversion (85–98%) of epoxy groups was obtained when the reaction was performed with an excess of the carboxylic acid at 100–120°C. The acrylate and methacrylate monomers of vernonia oil were characterized by IR and NMR spectroscopy. These monomers were then cured by sunlight in the presence of benzophenone to produce transparent films. In addition, interpenetrating polymer neworks (IPNs) were prepared in a two‐step technique from the sunlight‐cured methacrylate of vernonia oil, as the elastomeric component, in combination with a cured epoxy resin (a bisphenol A–type resin). Dynamic mechanical analysis showed good compatibility between the networks of the two cured polymers. An IPN with a 1 : 1 composition of the two polymer components exhibited the properties of a reinforced elastomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3835–3843, 2004     

Interpenetrating polymer networks from triglyceride oils containing special functional groups: A brief review1

Although most triglyceride oils contain only double bond functionality, a few oils such as castor oil, vernonia oil, lesquerella oil, etc., contain other functional groups. These functional groups include hydroxy and epoxy groups, permitting the easy formation of polyesters and/or polyurethanes. In addition to the natural formation of epoxy-bearing oils, the double bond functionality in ordinary triglyceride oils can be epoxidized. When these oils are polymerized to form polyesters or polyurethanes in the presence of polystyrene to synthesize interpenetrating polymer networks (IPN), a new class of tough plastics is formed.     

Synthesis and characterization of epoxy–silicone–polythiophene interpenetrating polymer network for corrosion protection of steel

Polymer alloys, particularly interpenetrating polymer networks (IPNs) exhibit excellent coating properties. Often combination of polymers result in IPNs with controlled morphologies and synergistic behavior. In this study, corrosion-resistant IPNs were prepared from immiscible resins (epoxy, silicone and thiophene) using a cross-linking agent and a catalyst. GPC, FTIR, NMR, TG, DTA and SEM studies used to fix the best performing IPN. Surface morphology studies using SEM confirm the incorporation of silicone and polythiophene in to the epoxy polymer to form homogeneously micro structured IPN. The heat-resistance of the IPN was determined as per ASTM 2485. The improved corrosion resistance of the IPN was evaluated by AC impedance measurements.     

Interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of two or more chemically distinct networks are not only intrinsically interesting as examples of macromolecular chemical topological isomerism but are in practice useful means of controlling mutual miscibility and phase morphology in crosslinked polymers. We will first review briefly the synthesis and properties of such IPN systems. This will be followed by an outline of a phenomenological theory of the phase stability and linearised theory of spinodal decomposition of binary, chemically quenched, low crosslink density IPNs recently developed by K. Binder and the author. Finally, we will discuss some aspects of the synthesis of ternary IPNs and the thermochromic properties of IPNs containing a crosslinked polydiacetylene.     

Gradient interpenetrating polymer networks. I. Poly(ether urethane) and polyacrylamide IPN

The swelling properties of poly(ether urethane)s and the preparation of interpenetrating polymer networks (IPNs) from a poly(ether urethane) thermoplastic elastomer and hydrogel forming polyacrylamide have been studied. The acrylamide monomer was polymerized with simultaneous crosslink formation, in the presence of the swollen thermoplastic elastomer. Upon removal of the swelling solvent, an IPN was obtained which absorbed water in the manner of a hydrogel but had mechanical properties superior to a hydrogel.     

Recent advances in interpenetrating polymer networks

We review the synthesis, morphology, and physical and mechanical properties of IFNs as well as the related pseudo-IPNs, in which only one of the polymers is crossliriked. Recent studies have shown that the degree of phase separation achieved in these materials is strongly dependent on the compatibility of blends of the linear polymer constituents of the IPN components as well as the kinetics of chain extension and the presence of grafting between component polymers. We illustrate this by a series of IPNs consisting of a polyurethane and an acrylic copolymer. The acrylic is a typical automotive enamel. An enhancement in properties results, which is dependent on the amount of grafting and the kinetics of polymerization. Also discussed are IPNs of a polyurethane and an epoxy, which exhibit a synergism in adhesive properties, and IPNs of a RIM polyurethane with several epoxies and unsaturated polyesters. In addition, also reported are the preliminary studies on the first successful preparation of a three-component IPN, consisting of a polyurethane, an epoxy, and an acrylic.     

Behavior of polyoxyethylene‐containing interpenetrating polymer networks and their LiCLO4 complexes as phase transfer catalysts and ionic conductors

Simultaneous grafted interpenetrating polymer networks (IPNs) based on [castor oil–poly(ethylene glycol) (PEG)] polyurethane and poly(alkyl methacrylate) were synthesized by simultaneously coupling castor oil and PEG with 2,4‐toluene diisocyanate and by radical polymerization of alkyl methacrylate with castor oil. The gel content of the IPNs is ～96% in most cases. The IPNs were characterized by infrared spectroscopy. The effects of compositional variation of the IPNs on phase transfer catalytic efficiency and mechanical properties, and conductivity of the IPNs complexed with LiClO₄ were also studied. The results show that the IPNs have good phase transfer catalytic ability in the Williamson reaction and exhibit a maximum conversion of potassium phenolate at 55% polyoxyethylene (PEO). The phase transfer catalytic ability of the IPN increases with molecular weight of PEG used in the IPN synthesis and with the length of alkyl groups of the grafts, but decreases with increasing crosslinking degree. The complex of the IPNs with LiClO₄ exhibits good ionic conductivity at room temperature in the range 10^?5–3 × 10^?4 S/cm. This ionic conductivity decreases with increasing either the crosslinking degree or the molecular weight of PEG used, but increases with increasing PEO content. The more compatible are the grafts with PEO, the lower is the conductivity. Either butyl methacrylate or ethyl methacrylate is a good choice for the monomer in the synthesis of the IPNs for use as phase transfer catalysts and ion conducting materials. The IPNs showed high tensile strength in the range 10–20 MPa. The good mechanical properties of the IPNs favor their applications as a strong solid polymer electrolyte film and an easily recoverable phase transfer catalyst. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 830–836, 2003     

Studies on castor oil–based polyurethane/polyacrylonitrile interpenetrating polymer network for toughening of unsaturated polyester resin

Tricomponent interpenetrating polymer network (IPN) systems involving castor oil, toluenediisocyanate (TDI), acrylonitrile (AN), ethylene glycol diacrylate (EGDA), and general‐purpose unsaturated polyester resin (GPR) were prepared with various compositions. The structures of the IPNs at various stages were confirmed using FTIR. The thermal stability of the IPNs was studied using TGA, which indicated that the polyurethane/polyacrylonitrile/GPR (PU/PAN/GPR) IPN underwent single‐stage decomposition, showing perfect compatibility at the IPN composition of 10 : 90 (PU/PAN : GPR). The mechanical properties such as tensile, flexural, impact, and hardness for the IPNs with various compositions were determined. It was found that the tensile strength of the GPR matrix was decreased and flexural and impact strengths were increased upon incorporating PU/PAN networks. The swelling properties in water and toluene were also studied. The morphology of the IPNs was studied using SEM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 817–829, 2004     

Conductive IPN based on polyaniline and silicon‐crosslinked styrene‐isoprene‐styrene triblock copolymer

A series of new conducting interpenetrating polymer networks (IPNs) are prepared by sequential crosslinking reactions of tetraethyl orthosilicate with silicon‐grafted functional styrene‐isoprene‐styrene triblock copolymer (SIS) and polyaniline (PANI) doped with dodecylbenzenesulfonic acid (DBSA). The various factors affecting the properties of conductive IPNs are investigated. The conductivity is found to increase only slightly after the IPN films are treated at 140 ° C . The thermal stability of the IPNs is much better than that of the pure polymer under nitrogen atmosphere, as shown by the results from thermal gravimetry analysis (TGA). © 1999 Society of Chemical Industry     

Preparation,morphology, and thermoelectric property studies of BaTiO3 superfine fiber/castor oil polyurethane‐based IPN nanocomposites

A series of castor oil polyurethane/poly(methyl methacrylate) interpenetrating polymer networks (IPNs) and gradient IPNs, cured at room temperature, were prepared by a simultaneous IPN method. The polymerization processes were traced through IR techniques; results for the morphology and miscibility among multiple phases of materials, obtained by transmission electron microscopy, indicated that the systems belonged to graft‐mode IPNs, and the domains between two phases were controlled on a nanometer scale. Thermomechanical analysis detection results showed that through interpenetration between networks, the glass‐transition temperatures of the systems could be linked up effectively. Furthermore, the systems were combined with selected barium titanate superfine fibers. The composite techniques were determined, and the thermoelectric and mechanical properties were examined in detail. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 709–715, 2002; DOI 10.1002/app.10024     

Study on the properties,morphology, and applications of castor oil polyurethane—poly(methyl methacrylate) IPNs

A series of castor oil polyurethane—poly(methyl methacrylate) interpenetrating polymer networks (IPN COPU/PMMA) were produced from castor oil, toluene diisocyanate, and methyl methacrylate. The properties and morphology of the IPNs were estimated. The adhesives based on the IPN COPU/PMMA prepolymer were prepared and the influence of the composition on the adhesion strength was studied. The experimental results showed that the adhesives have an effective adhesive power for metals and these adhesives have good prospects in a practical project. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1393–1401, 1997     

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     

Curing and mechanical properties of dicyanate/poly(ether sulfone) semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) composed of a dicyanate resin and a poly(ether sulfone) (PES) were prepared, and their curing behavior and mechanical properties were investigated. The curing behavior of the dicyanate/PES semi‐IPN systems catalyzed by an organic metal salt was analyzed. Differential scanning calorimetry was used to study the curing behavior of the semi‐IPN systems. The curing rate of the semi‐IPN systems decreased as the PES content increased. An autocatalytic reaction mechanism was used to analyze the curing reaction of the semi‐IPN systems. The glass‐transition temperature of the semi‐IPNs decreased with increasing PES content. The thermal decomposition behavior of the semi‐IPNs was investigated. The morphology of the semi‐IPNs was investigated with scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1079–1084, 2003     

Cure kinetics and physical properties of dicyanate/polyetherimide semi‐IPNs

The curing behavior and physical properties of dicyanate/polyetherimide (PEI) semi‐interpenetrating polymer network (IPN) systems were investigated. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/PEI semi‐IPN systems. The curing rate of the semi‐IPN system decreased as the PEI content increased. An autocatalytic reaction mechanism can describe well the curing kinetics of the semi‐IPN systems. The reaction kinetic parameters were determined by fitting DSC conversion data to the kinetic equation. The glass transition temperature of the semi‐IPNs decreased with increasing PEI content. Two glass transitions due to phase‐separated morphology were observed for the semi‐IPN containing over 15 phr (parts per hundred parts of dicyanate resin) PEI. The thermal stability and dynamic mechanical properties of the semi‐IPNs were measured by thermal analysis.     

Ionomer interpenetrating polymer networks from polyurethane anionomers and polyurethane isocyanurate

Two-component interpenetrating polymer network (IPN) systems composed from polyurethane isocyanurate and polyurethane anionomer were prepared by simultaneous polymerization and crosslinking in solution. Specific attractive forces that occurred among various networks helped to make them compatible and led to the formation of true homogeneous topologically interpenetrating polymer networks. These ionomer IPNs were characterized by means of stress-strain properties, hardness, thermogravimetric analysis, density and conductivity. The morphology of the IPNs was studied by thermomechanical analysis and dynamic mechanical analysis.     

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.     

Development and characterization of thermosensitive hydrogels based on poly(N‐isopropylacrylamide) and calcium alginate

This work refers to the synthesis and characterization of thermosensitive hydrogels based on interpenetrating polymer networks (IPNs) of poly(N‐isopropylacrylamide) (PNIPAAm) and calcium alginate in the form of films. The influence of the crosslinking degree of PNIPAAm and alginate content on thermal, swelling, mechanical, and morphological properties of hydrogels is investigated in detail. Characterization of pure PNIPAAm hydrogels and IPN hydrogels was performed by FTIR, DSC, DMA, and SEM. In addition, the studies of equilibrium swelling behavior as well as swelling, deswelling, and reswelling kinetics are performed. The results obtained imply the benefits of synthesizing IPNs based on PNIPAAm and calcium alginate over pure PNIPAAm hydrogels. The presence of calcium alginate contributes to the improvement of mechanical properties, the deswelling rate of hydrogels, and the network porosity, without altering the thermosensitivity of PNIPAAm significantly. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Epoxy/castor oil graft interpenetrating polymer networks

Full-interpenetrating polymer networks (IPNs) were prepared from epoxy and castor oil-based polyurethane (PU), by the sequential mode of synthesis and were characterized by different techniques: swelling test, scanning electron microscopy (SEM), thermomechanical analysis (TMA), thermogravimetric analysis (TGA), tensile test, and instrumented impact test. 2,4-Toluene diisocyanate (TDI) was used as a curing agent for castor oil, at a NO/OH ratio = 1.50. Diglycidyl ether of bisphenol A (DGEBA) was cured and crosslinked using 2,4,6-tris(dimethylaminomethyl)phenol (TDMP) at 1.5%, by weight, of epoxy resin. The homogeneous morphology of IPN samples of PU compositions up to 40%, by weight, revealed by SEM may be attributed to some extent to grafting of the PU phase onto the epoxy matrix, which results from the reaction between NCO groups in the PU phase with OH groups in the epoxy matrix. This has some synergistic effect on the thermal resistance and tensile properties of IPNs compared to those of the pure components, such as illustrated by the data from TGA and tensile tests. However, the grafting structure appears not to enhance their impact resistance, which probably requires the formation of rubbery particles of suitable size. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1649–1659, 1998     

Polysiloxane-Cellulose acetate butyrate cellulose interpenetrating polymers networks close to true IPNs on a large composition range. Part II

Interpenetrating polymer networks combining cellulose acetate butyrate (CAB) and α,ω-divinyl-polydimethylsiloxane (PDMS) in different weight proportions have been synthesized. The synthesis involves a one pot-one shot process in which all components are first mixed together. For each composition, the relative CAB and PDMS network formation rates are adjusted through the concentration of DBTDL used as CAB network formation catalyst. Thus, the chemically independent networks are formed quasi-simultaneously in order to avoid phase separation. The CAB cross-linking density effect on the PDMS/CAB IPN mechanical properties has also been particularly studied. All synthesized IPNs are transparent and only one mechanical relaxation temperature lying between those of the single CAB and PDMS networks is observed by DMTA analysis. These results show that the networks are correctly interpenetrated and no phase separation is observed at the DMTA level. Some mechanical properties of the PDMS network are significantly improved in this IPN combination and their stress-strain behavior has highlighted a synergistic effect arising from the IPN architecture. Thus, these IPNs exhibit many characteristics, which would allow defining them as close to ‘true’ IPNs.