Dielectric studies of chain dynamics in homogeneous semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) were prepared from linear polyurethane (PUR) and polycyanurate (PCN) networks. Wide‐angle X‐ray scattering measurements showed that the IPNs were amorphous, and differential scanning calorimetry and small‐angle X‐ray scattering measurements suggested that they were macroscopically homogeneous. Here we report the results of detailed studies of the molecular mobility in IPNs with PUR contents greater than or equal to 50% via broadband dielectric relaxation spectroscopy (10⁻²–10⁹ Hz, 210–420 K) and thermally stimulated depolarization current techniques (77–320 K). Both techniques gave a single α relaxation in the IPNs, shifting to higher temperatures in isochronal plots with increasing PCN content, and provided measures for the glass‐transition temperature (T_g) close to and following the calorimetric T_g. The dielectric response in the IPNs was dominated by PUR. The segmental α relaxation, associated with the glass transition and, to a lesser extent, the local secondary β and γ relaxations were analyzed in detail with respect to the timescale, the shape of the response, and the relaxation strength. The α relaxation became broader with increasing PCN content, the broadening being attributed to concentration fluctuations. Fragility decreased in the IPNs in comparison with PUR, the kinetic free volume at T_g increased, and the relaxation strength of the α relaxation, normalized to the same PUR content, increased. The results are discussed in terms of the formation of chemical bonds between the components, as confirmed by IR, and the reduced packing density of PUR chains in the IPNs. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3070–3087, 2000     

Physico-mechanical and WAXS studies of PU/PS semi interpenetrating polymer networks

The polyethylene glycol (PEG) based polyurethane (PU) and its semi interpenetrating polymer networks (SIPNs) with polystyrene (PS) were prepared. The FTIR, physico-mechanical properties like density, tensile strength, percentage elongation at break and surface hardness of the IPNs were measured. Wide angle X-ray studies (WAXS) were made to know the microcrystalline parameters such as crystal size (〈N〉), lattice disorder (g), surface (D_s) and volume (D_v) weighted crystal size of SIPNs. The different asymmetric column length distribution functions were employed using Exponential, Lognormal and Reinhold methods and the results are compared.     

Epoxy/SiO2 interpenetrating polymer networks

We demonstrate a potentially useful method of generating an SiO₂ morphology, in situ, with interpenetrating polymer networks (IPN) chemistry. Organic/inorganic IPNs were synthesized with an organic phase made of epoxy resin and an SiO₂ phase made by sol—gel chemistry. The two types of polymerization used were sequential and simultaneous with SiO₂ content ranging from 0.02 to 0.43 g SiO₂/g total weight. The resultant morphologies were examined by small angle X-ray scattering and transmission electron microscopy. The sequential IPNs were strongly phase separated into a finely divided SiO₂ phase of ∼10 nm size scale. The simultaneous IPNs were weakly phase separated with considerable mixing in the phases. Thermal studies showed increased thermal stability for the IPNs, compared with unfilled epoxies or physically mixed silica filled epoxies.     

Polyurethane/polyethyl acrylate interpenetrating polymer networks

The thermal decomposition kinetics of polyurethane/polyethyl acrylate interpenetrating polymer networks (PU/PEA IPN) were studied by means of thermogravimetry and derivative thermogravimetry (TG-DTG), and compared with those of polyurethane (PU) and polyethyl acrylate (PEA). The decomposition temperature (T _i) of PU/PEA IPN was found to be higher thanT _i of PEA, but lower thanT _i of PU. Thermal decomposition kinetic parameters,n andE, estimated using Coats-Redfern method, are found for PU/PEA IPN, PU and PEA to be 1.6, 1.9 and 1.1, and 196.6, 258.6 and 139.2 kJ mol^–1, respectively. The results show that PU/PEA IPN is neither a simple mixture of PU and PEA nor a copolymer of them. The mechanism of thermal decomposition of PU/PEA IPN is different from those of PU and PEA. The special network in PU/PEA IPN effectually protects weak bonds in the molecular chain of PU and PEA.We express our thanks to Dr. Yaxiong Xie and Zhiyuong Ren for their help in this work,     

Damping characteristics and mechanical properties of silica filled PUR/PEMA simultaneous interpenetrating polymer networks

Simultaneous polyurethane/poly(ethyl methacrylate) interpenetrating polymer network was synthesised by the one-shot route at the 70PUR/30PEMA composition ratio. This semi-miscible IPN exhibited its potential as a material for damping application by a broad loss factor (tan δ) ? 0.3 spanning a temperature range of 132 °C. The TEM micrographs revealed a multiphase morphology where the mixing between the two polymers was extensive. Incorporation of silica was made in order to study the effects of filler on the IPN properties in terms of glass transition temperature, dynamic mechanical properties, and mechanical and thermal properties. Dynamic mechanical thermal analysis indicated that the filler enhanced the damping ability of the IPN at certain temperature range. Furthermore, the addition of filler resulted in improved material strength.     

Structure of interpenetrating polymer networks

A possible model for the formation of interpenetrating polymer networks is suggested. Phase separation is assumed to be faster than gelation. This implies that domains rich in either component grow first until late stages of spinodal decomposition. In these domains, short linear chains are crosslinked, leading to large branched macromolecules. Growth of the domains is slowed down by the presence of crosslinked polymers. It is assumed that it is stopped when the sizes of the domains and of the branched macromolecules are comparable. The resulting domains are significantly larger than the average distance between crosslinks. These results are supported by recent neutron scattering results on a poly(carbonate-urethane)/polyvinyl pyridine interpenetrating network. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1507–1512, 1998     

Swelling of interpenetrating polymer networks

We have studied the densities, kinetics, and equilibrium degree of swelling in a number of different solvents of poly(carbonate urethane)/poly(methyl methacrylate) and poly(carbonate urethane)/poly(vinyl pyridine) interpenetrating polymer networks (IPN's). The kinetics of solvent uptake are often anomalous. The equilibrium extent of swelling reflects, among other factors, the number of phases present. © 1993 John Wiley & Sons, Inc.     

A review of kinetic studies on the formation of interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) are unique alloys of crosslinked polymers. This article reviews the studies on kinetic effects involved in IPN formation. Several investigators have studied the effect of kinetics of curing reactions on the morphology and properties of IPNs. It was found, in general, that the faster the rates of the respective chain extension and crosslinking reactions are and the closer they are to simultaneity, the more homogeneous are the IPNs. Other investigations revealed that the individual components sometimes can polymerize more rapidly in the IPN than alone, due to a “solvent effect” of the IPN. Effects of changing reaction variables, such as NCO/OH ratio, composition activators and temperature were used to study reaction kinetics as well as phase morphology by the Fourier transform infrared technique. Thermochemical techniques have been utilized to study the kinetics of IPN formation which influence phase separation. Small-angle X-ray scattering and small-angle neutron scattering techniques were used to estimate the extent of microheterogeneity of the phase domains in a study of the kinetics of phase separation in the IPNs.     

聚氨酯/环氧树脂互穿网络聚合物的性能研究

互穿聚合物网络（Interpenetrating polymer net-work,简称IPN）广泛应用的为聚氨酯基的互穿网络聚合物。其合成多集中在弹性体方面。本文用同步法合成的聚氨酯／环氧树脂互穿网络硬质泡沫塑料材料（简称PU／ERIPNF）,机械性能较好,并研究了其动态力学性能及形态变化。     

Graft interpenetrating polymer networks of polyurethane and epoxy. I. mechanical behavior

Polyurethanes (PU) based on poly(butylene adipate) [PU(PBA)] and poly(oxypropylene) [PU(PPG)] polyols have bean introduced into the diglycidyl ether of bisphenol A (epoxy) to form interpenetrating polymer networks (IPNs) with a PU-grafted epoxy structure (graft-IPNs). The tensile strength in both PU(PPG)/epoxy and PU(PBA)/epoxy systems increases with increasing PU content. Maximum values emerge at PU/epoxy ratios between 19/81 and 27/73. This is explained as a result of the presence of the graft structure, which leads to more intimate interpenetration between the PU and epoxy in the graft-IPNs. Dynamic mechanical analysis (DMA) indicates that the PU introduced can be incorporated in either the α or β transition domain of the epoxy. The tensile strength of the resulting graft-IPNs shows a significant improvement as the PU is incorporated in the α transition domain of the epoxy. It is also noted that suitable amounts of PU incorporated in both the α and β transition domains of epoxy can increase the tensile strength of the IPNs, while excessive amounts of PU introduced into both α or β transition domains tend to decrease the tensile strength of the graft-IPNs.     

Synthesis and properties of miscible epoxy/acrylic interpenetrating polymer networks

Three series of epoxy/acrylic interpenetrating polymer networks were prepared by the simultaneous polymerization of diglycidyl ether of bisphenol A, crosslinked with an aliphatic diamine, diglycidyl ether of bisphenol A dimethacrylate, bisphenol A dimethacrylate, and diethoxy bisphenol A dimethacrylate. Under the conditions provided it is believed that the two networks form simultaneously but independently. Differential scanning calorimetry and dielectric measurements indicate that these polymer networks are miscible because they exhibit a single, sharp glass transition temperature, the values of which, however, are lower than predicted by the law of mixture. This decrease may be due in part to the dilution of one network by the other and to the resulting breakage of intramolecular interactions. It is also due, in part or in whole, to the presence of solvent and/or monomer impurities that act as plasticizers.     

Nylon 6/polyisocyanurate interpenetrating polymer networks (IPNs)

Two component interpenetrating networks (IPNs) of the SIN type (simultaneous interpenetrating networks), composed of a polyisocyanurate network and a star-shaped nylon 6, were made. The overall polymerization rates and physical properties for reaction injection molding (RIM) have been studied by the quasi-adiabatic process. In order to model the actual rapid molding conditions, time versus temperature reaction profiles were measured, and the relative rates of polymerization subsequently determined from these data.     

Pseudo interpenetrating polymer networks and interpenetrating polymer networks of zeolite 13 X and polystyrene and poly(ethyl acrylate)

Free-radical polymerization of liquid styrene and ethyl acrylate with or without ethylene dimethacrylate crosslinker in the presence of zeolite 13 X produces interpenetrating polymer networks (IPN's) or pseudo IPN's in which polymer chains have grown and filled internal pores of the zeolite. A variety of methods of characterization including, solubility studies, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), ¹³C solid-state nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) provide supporting evidence for this. The polymer chains within the internal pores do not exhibit a bulk glass transition. This is part of a larger study of the glass transition of polymers confined to cavities or pores of various sizes.     

The current status of interpenetrating polymer networks

An interpenetrating polymer network, IPN, is defined as a combination of two or more polymers in network form, at least one of which is polymerized and/or crosslinked in the immediate presence of the other(s). The synthesis, morphology and mechanical properties of recent works are reviewed, with special emphasis on dual phase continuity, and the number of physical entanglements that arise in homo-IPNs. The concepts of phase diagrams are applied, especially to simultaneous interpenetrating network phase separations and gelations. Recent engineering applications are discussed.     

On microphase segregation of interpenetrating polymer networks

The topological entanglements between subchains of two interpenetrating polymer networks are described in the simplest approximation supposing that the primitive path of each subchain is influenced due to the shift of one network relatively to the other. The entanglement contribution to the free energy of the networks is shown to behave as 1/q² for the state with deviation from uniform densities with the wave vector of order q. This contribution is shown to cause the microphase type of segregation.     

Hydrophilic-hydrophobic interpenetrating polymer networks and dicyanate-based semi-ipn materials

Hydrophilic-hydrophobic IPN materials of poly(acrylic acid)-poly(styrene-co-acrylonitrile) were synthesized and the pervaporation characteristics of the IPN membranes were evaluated for the separation of ethanol/water mixture. Hydrophilic-hydrophobic IPN materials of polyurethane-polystyrene were synthesized and the blood compatibility of the IPN's were measured for the biomedical application. Dicyanate-engineering plastics semi-IPN's were prepared and the morphology and mechanical properties were evaluated for the high temperature composite matrix materials.     

Epoxy-poly(2-ethylhexyl acrylate) interpenetrating polymer networks morphology and mechanical and thermal properties

Full and semi-IPNs of Poly(2-ethylhexyl acrylate), PEHA & crosslinked epoxy homopolymer were prepared and characterized by measurements of mechanical, thermal and morphological properties. Aromatic polyamine adducts and ethylene glycol dimethacrylate were used as the cross-linker for epoxy and comonomer/cross-linker for 2-ethyl hexyl acrylate monomer. Effects of changes of blend ratio on the properties were examined. Semi-IPNs were characterized by higher tensile strength and modulus than the corresponding full IPNs. Both semi- and full IPNs were characterized by broadening of transitions in their respective DSC curves while the weight retention in the thermal decomposition of the IPNs and pseudo-IPNs was higher than the epoxy homopolymer network. Phase separated rubber domains of various sizes are presumed to be responsible for the increased toughness of poly(2-ethyl hexyl acrylate)-modified epoxy which is substantiated by SEM micrographs.     

Bioactive interpenetrating polymer networks for improving the electrode/neural-tissue interface

The neural electrode is recognized as a bridge that transduces electrical signals from or into biosignals and is thus used for various experimental and therapeutic purposes. However, a major challenge that still remains is to achieve long-term effective electrical recording and stimulation in vivo. Here, we report an investigation of electrochemically co-deposited poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/nerve growth factor/dexamethasone phosphate/poly(vinyl alcohol)/poly(acrylic acid) interpenetrating polymer networks for improving the electrode/neural-tissue interface. After modification, the electrodes exhibit a substantially higher capacitance and lower electrochemical impedance (reduced by ~ 96%) at 1 kHz as compared to control electrodes. Furthermore, tissue response was evaluated after a 6-week implantation in the cortex of rats. Relative to the control group, the test group show significantly lower immunostaining intensity for glial fibrillary acidic protein and higher intensity for neuronal nuclei at the electrode/neural-tissue interface. All of these characteristics are greatly desired in chronic electrophysiological applications in vivo.     

Synthesis and characterization of polyaniline filled PU/PMMA interpenetrating polymer networks

A series of conducting interpenetrating polymer networks (IPNs), are prepared by sequential polymerization of castor oil based polyurethane (PU) with poly(methyl methacrylate) (PMMA) and polyaniline doped with camphor sulphonic acid (PAni)_CSA. The effect of different amount of PAni (varies from 2.5-12.5%) on the properties of PU/PMMA (50/50) IPNs such as electrical properties like conductivity, dielectric constant and dissipation factor; mechanical properties like tensile strength and percentage elongation at break have been reported. (PAni)_CSA filled IPNs shows improved tensile strength than the unfilled IPN system. The thermal stability and surface morphology of unfilled and (PAni)_CSA filled PU/PMMA (50/50) IPN sheets were investigated using a thermogravimetric analyzer (TGA) and a scanning electron microscope (SEM). TGA thermograms of (PAni)_CSA filled PU/PMMA (50/50) IPNs show a three-step thermal degradation process. SEM micrograms of filled PU/PMMA IPN system shows spherulitic structure at higher concentration of (PAni)_CSA.     

Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.