Kinetic study of simultaneous interpenetration polymer network Based on polyurethane and poly(ethylene glycol) diacrylate

Poly(ethylene glycol) diacrylate (PEGDA) was synthesized by reacting poly(ethylene glycol) and acrylol chloride. PEGDA network formation was induced by using benzoyl peroxide (BPO) as a curing agent. Polyurethane (PU) network was prepared by reacting equimolar amounts of trimethylol propane (TMP) and desmodur L. Simultaneous interpenetrating polymer network (SIN) was prepared by using the same curing method. Changes of functional groups were monitored by FTIR. Kinetic study of the SIN formation was done at 70, 75, 80, and 85 °C. The kinetic parameters were compared with those of the respective PEGDA and PU network formation. Experimental results revealed that SIN indicated a lower rate constant and a higher activation energy than the respective pure PEGDA and PU components. A network interlock effect was proposed to explain the observed phnomenon.     

Synthesis of biodegradable PU/PEGDA IPNs having micro-separated morphology for enhanced blood compatibility

Summary New biodegradable hydrophobic polyurethane (PU)/hydrophilic poly (ethylene glycol) diacrylate (PEGDA) IPN was simultaneously synthesized with changing the molecular weight of PEGDA to investigate the effect of crosslinking density on the degree of phase separation. PU was modified using biodegradable poly(-caprolactone)diol and the hydroxy group of PEG was substituted to crosslinkable acrylate group having double bond, which induce photo-polymerization. The sturucture of PEGDA was confirmed by NMR. Because the reaction rate of PEGDA was faster than that of PU, the continuous matrix of the micro-separated PU/PEGDA IPNs having amphiphilic character was made of hydrophilic PEGDA-rich phase. All IPNs have sea-island morphology resulting from the suppressed phase separation. The effect of the degree of phase separation on blood compatibility was investigated.     

Curing behaviour of compatible interpenetrating polymer networks based on epoxy and methacrylated epoxy

Compatible interpenetrating polymer networks (IPNs) based on diglycidyl ether of bisphenol A (DGEBA) and methacrylated diglycidyl ether of bisphenol A (MADGEBA) in weight ratios of 100/0, 75/25, 50/50, 25/75 and 0/100 were blended and cured simultaneously by using dicumyl peroxide (DICUP) and hexahydrophthalic anhydride (HHPA) as curing agents. Fourier transform infrared spectroscopy (FTIR) was employed to investigate the intermolecular interactions and functional group changes. Viscosity increases during crosslinking were examined with a Brookfield viscometer. Curing exothermic peaks were studied with differential scanning calorimetry (DSC). The gel fractions of various IPN compositions were measured with a Soxhlet extractor. Samples thus prepared were checked for their compatibility by measuring glass transitions with DSC and damping peaks with rheometric dynamic spectroscopy (RDS). Experimental results revealed that good compatibility between components induced a network interlock, which subsequently resulted in incomplete cure of the IPN materials. ©1997 SCI     

Semi‐IPN asymmetric membranes based on polyether imide (ULTEM) and polyethylene glycol diacrylate for gaseous separation

Semi‐interpenetrating polymer networks (semi‐IPN) formed with commercial polyether imide (ULTEM®, PEI) and poly (ethylene glycol) diacrylate (PEGDA) were used to make asymmetric membranes. The effect of increasing amount of PEGDA on the bulk and the gas separation properties of semi‐IPN membranes were studied. The formation of IPNs was confirmed by Fourier Transform Infra Red (FT‐IR) spectroscopy. The 5% weight loss temperature decreased and the percent weight loss of the first step increased with increase in the PEGDA content, which indicated the incorporation of more poly (ethylene glycol) (PEG) segments to the semi‐IPNs. The microscopic experiments revealed the change in morphology with change in PEGDA content. The Scanning electron micrographs exhibited typical finger‐like voids in the sub layer, which is characteristic morphology of asymmetric membranes. The increase in PEGDA content up to 5.7 wt % increased the CO₂/N₂ selectivity of the semi‐IPN after which the selectivity decreased and permeance increased. Although, the increase in the polar poly (ethylene glycol) molecules is expected to render better CO₂ selectivity, the performance of the membrane was found to decrease as PEGDA content exceeded 5.7% for the given ratio. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of interpenetrating polymer networks from polyurethane and poly(ethylene glycol) diacrylate

Interpenetrating polymer networks (IPNs) combining polyurethane (PU) and poly(ethylene glycol) diacrylate (PEGDA) networks were prepared with simultaneous polymerization. PU was synthesized from biocompatible and biodegradable poly(ε-caprolactone) diol, and the hydroxyl group of poly(ethylene glycol) was substituted with a crosslinkable acrylate group. The effects of the PU/PEGDA compositions and the crosslink density of PU and PEGDA on the thermal properties, swelling ratio, surface energy, mechanical properties, and morphologies were investigated. The mechanical properties of PEGDA networks were improved by the presence of PU networks, particularly in the 75% PU/25% PEGDA IPNs. All PU/PEGDA IPNs showed a microphase-separated structure with cocontinuous morphology, as observed by atomic force microscopy, which was in agreement with the results of swelling ratio and dynamic mechanical thermal analysis measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semi-IPNs formed from poly(ethylene glycol monomethyl ether acrylate) and an epoxy thermoset

Poly(ethylene glycol monomethyl ether acrylate) (PEGMEA) was synthesized from the reaction of poly(ethylene glycol monomethyl ether) (PEGME) with acryloyl chloride. Semi-IPNs based on various weight ratios of diglycidyl ether of bisphenol A (DGEBA)/PEGMEA were prepared, using isophronediamine (IPDA) and 2,2′-azo-bis(isobutyronitrile) (AIBN) as curing agents. The glass transition temperature and exothermic peak shifts were studied with differential scanning calorimetry (DSC). Viscosity changes during semi-IPN formation were measured with a Brookfield viscometer. Dynamic mechanical properties were investigated by rheometric dynamic spectroscopy (RDS). Stress–strain curves were obtained with an Instron tensile tester, while impact resistance was measured with a computer aided falling dart impact tester. Experimental results revealed retarded curing rates for all semi-IPNs, as evidenced from the shifts of curing exothermic peaks to higher temperatures, together with retarded viscosity increases during semi-IPN formation. These phenomena were interpreted in terms of chain entanglement between epoxy and PEGMEA. Nevertheless, the semi-IPNs indicated good compatibility as inferred from a single T_g in DSC and a single damping peak in RDS for each semi-IPN. Improved tensile stress and strain along with toughness improvements were noticed for this semi-IPN system. Shear band yielding was proposed to interpret this result. © 1999 Society of Chemical Industry     

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     

Dynamic mechanical properties of interpenetrating polymer networks of polyurethane and poly(styrene-co-acrylonitrile)

Summary Interpenetrating polymer networks (IPN's) of a combination of polyurethane (PU) and poly(styrene-co-acrylonitrile) (PSAN) were prepared by the simultaneous polymerization process. To observe the relative rate effect of the simultaneous polymerization, the polymerization kinetics of PU and PSAN were studied. The gel-times of PU and PSAN network were theoretically calculated, and three types of SIN's with different rates of network formation in each component were prepared for comparison. IPN's with Mc=3000 and Mc=4900 were prepared to observe the influence of the crosslink density. The glass transition behavior studied by the dynamic mechanical analysis showed larger shifts in Tg's in SIN's with similar gel-times and smaller Mc.     

聚氨酯／呋喃树脂互穿聚合物网络性能的研究

用糠醇型呋喃树脂或ＨＦ９２００Ａ环氧型呋喃树脂与聚环氧丙烷醚型聚氨酯制备了互穿聚合物网络（ＩＰＮ）。通过红外光谱和扫描电子显微镜分析了聚氨酯（ＰＵ）／呋喃树脂（ＦＡ）ＩＰＮ网络形成的动力学和微相分离行为，并考察了不同配比下ＩＰＮ的力学性能。实验结果表明，ＰＵ／ＦＡ达到某一比值时，产生互穿聚合物网络的协同效应，可改善聚氨酯的刚性，提高呋喃树脂的抗冲击等性能     

Fabrication of Shape‐Memory Aerogel Based on Chitosan/Poly(ethylene glycol) Diacrylate Semi‐Interpenetrating Networks via a Facile and Eco‐Friendly Strategy

While the field of shape memory polymers (SMPs) has developed rapidly, it is still highly challenging to obtain SMPs in the form of aerogels (SMPAs) due to the unique technique used for the fabrication of the aerogels and their high porosity. Herein, a thermally induced SMPA based on chitosan/poly(ethylene glycol) diacrylate (CS/PEGDA) semi‐interpenetrating networks is reported that are produced using an eco‐friendly strategy. The main network is responsible for the shape memory effect (SME) and can be easily tuned by varying the feed ratio of the two PEGDA precursors, which have different molecular weights. The crystalline segment in poly(ethylene glycol) diacrylate (PEGDA) with higher molecular weight acts as the molecular switch, and the PEGDA with lower molecular weight endows the network with an efficient degree of crosslinking. Meanwhile, the chitosan (CS) is interpenetrated into the main network to enhance the aerogel. The SME is realized both at the macroscale and the microscale, as is further demonstrated for three different models with various shapes.     

Enhanced adsorption properties of interpenetrating polymer network hydrogels for heavy metal ion removal

In this study, sequential interpenetrating polymer network (IPN) hydrogels based on poly(polyethylene glycol diacrylate) poly(PEGDA) and poly(methacrylic acid) (PMAA) were prepared with enhanced adsorption properties for heavy metal ion removal. The swelling behavior and mechanical property of the IPN hydrogels were characterized. It was found that swelling ratio increased, and mechanical strength decreased with the PMAA content in the IPN. The IPN hydrogels were used to remove heavy metal ions from aqueous solution under the non-competitive condition. The effects of pH values of the feed solution at the range of 3–5 and PMAA content in the IPN on the adsorption capacity were investigated. The results indicated that the adsorption capacity of the IPN hydrogels increased with the pH values and PMAA content in the IPN. Furthermore, the synergistic complexation of metal ions with two polymer networks in the IPN was found in the adsorption studies. Regeneration studies suggested that metal rebinding capacity of the IPN hydrogels did not change significantly through repeated applications compared with the first run. It was concluded that the poly(PEGDA)/PMAA hydrogels could be used as fast-responsive, high capacity, and renewable sorbent materials in heavy metal removing processes.     

Acoustical,damping and thermal properties of polyurethane/poly(methyl methacrylate)-based semi-interpenetrating polymer network foams

In the present study, the interpenetrated polymer networks (IPN) foams of polyurethane (PU) and poly(methyl methacrylate) (PMMA) with different ratio of PU/PMMA (i.e. 85/15, 75/25 and 65/35) were prepared using the polymerisation process. The acoustical, damping and thermal properties of synthesised IPN foams with regard to different compositions were studied. As indicators of effective damping capability, viscoelastic parameters including loss factor (tan δ), glass transition temperature (T_g) and effective damping interval (tan δ?>?0.3) were also determined. The results show that the T_g shifted to higher temperature ranges, and the damping temperature range (tan δ?>?0.3) increased when the IPN was formed. The sound absorption coefficient results show that because of the formation of IPN, the sound-absorbing capacity of prepared samples increased at a certain frequency, and the resonance frequency shifted to lower frequencies by increasing the PMMA content in IPN foams.     

聚氨酯/乙烯基酯树脂互穿聚合物网络泡沫性能研究

研究了两种不同固化体系对乙烯基酯树脂(VER)的固化和对聚氨酯(PU)网络的匹配,以及单体结构和配比对PU/VERIPN硬质泡沫塑料力学性能和阻尼性能的影响规律。确定了过氧化二苯甲酰和N,N-二甲基苯胺合用的固化剂体系。实验表明,增加IPN中PU网络的高羟值聚醚(N303)的添加量,PU/VERIPN泡沫材料的压缩强度和压缩模量增大,冲击强度下降。S组的泡沫塑料的VER和PU具有较好的相容性,其Tanδ曲线出现一个很宽的阻尼平台,表现出较好的低温阻尼性能。     

PU/EP/PPGDA三元IPN弹性体的结构研究

用红外光谱 (IR)、扫描电子显微镜 (SEM )、X光电子能谱 (XPS)研究了以聚氨酯 (PU)为第一网络的三元IPN聚氨酯 /环氧树酯 /聚丙二醇二丙烯酸酯 (IPNPU/EP/PPGDA)弹性体的互穿特性和形态结构。研究结果表明 ,各元素在三元IPN表面和内部分布不一致 ,表明三种聚合物在IPN中的分布是不均匀的 ,这种差异与IPN组成、组成聚合物间的相容性以及形态结构有密切联系     

Synthesis and characterization of nanocomposites of silicon dioxide and polyurethane and epoxy resin interpenetrating network

Nanocomposites with varying concentrations of nanosized silicon dioxide particles were prepared by adding nanosilica to interpenetrating polymer networks (IPN)s of polyurethane and epoxy resin (PU/EP). The PU/EP IPNs and nanocomposites were studied by dynamic mechanical analysis, scanning electronic microscopy, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The result showed that adding nanosize silicon dioxide can improve the properties of compatibility, damping and phase structure of IPN matrices. Copyright © 2003 Society of Chemical Industry     

Interpenetrating polymer network and nanocomposite IPN of polyurethane/epoxy: a review on fundamentals and advancements

This article presents state-of-the-art review on interpenetrating polymer network (IPN) formation by polyurethane/epoxy (PU/EP). PU is thermoplastic polymer with fine mechanical strength, chemical resistance, processability, and thermal stability. EP resins also possess unique chemical and physical properties, though it is rigid and brittle. Amalgamation of two polymers have resulted in improved mechanical, thermal, damping, and glass transition behavior. PU/EP IPN and nanocomposite containing carbon nanotube, graphene oxide, nanodiamond, nanoclay, and various other nanoparticles have been discussed. Commercial implication and future prospects of PU/EP-crosslinked network and nanocomposite IPN are foreseen in high-performance engineering materials, automotive and aerospace, and biomedical devices.     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

Chemorheology on simultaneous IPN formation of epoxy resin and unsaturated polyester

Study of the simultaneous interpenetrating polymer network (IPN) between diglycidyl ether of bisphenol-A (DGEBA) and unsaturated polyester (UP) was carried out at ambient temperature. Fourier transform infrared (FTIR) spectroscopy was employed to investigate the intermolecular H-bonding and functional group changes. Viscosity changes due to H-bonding and crosslinking were examined with a Brookfield viscometer. Gelation time was measured by a Techne gelation timer. Complexation between Co(II) (the promoter for UP cure) and diamine (the curing agent for DGEBA) was detected with UV-visible spectrometer. Experimental evidence revealed that intermolecular interactions were observed in systems such as DGEBA/UP, DGEBA/diamine, Co(II)/diamine, DGEBA/uncured UP, and UP/uncured DGEBA. All such interactions had measurable effects on the curing behaviors for both networks, as were indicated by the viscosity changes and gelation time. The IPNs thus obtained were further characterized with rheometric dynamic spectroscopy (RDS) and differential scanning calorimetry (DSC). Partial compatibility between UP and DGEBA networks was evidenced from a main damping peak with a shoulder near glass transition temperature (T_g) for lower UP content; while at higher UP content, only a main damping peak near T_g was observed. DSC revealed a broad glass transition for all IPNs. The resultant IPN materials were all transparent. © 1992 John Wiley & Sons, Inc.     

Poly(ethylene oxide)/polybutadiene based IPNs synthesis and characterization

Interpenetrating polymer networks (IPNs) were prepared from hydroxytelechelic polybutadiene (HTPB) and poly(ethylene oxide) (PEO) via an in situ process. The PEO network was obtained by free radical copolymerization of poly(ethylene glycol) methacrylate and dimethacrylate. Addition reactions between HTPB and a pluri-isocyanate cross-linker (Desmodur^® N3300) led to the HTPB network. Polymerization kinetics were followed by Fourier transform spectroscopy in the near and middle infrared. Mechanical properties and the IPN morphology were investigated by dynamic mechanical analysis and transmission electron microscopy. The relation between the formation rates of the two networks and the IPN final morphology is discussed.     

Sulfonated polyimide and poly (ethylene glycol) diacrylate based semi‐interpenetrating polymer network membranes for fuel cells

Semi‐interpenetrating polymer network (semi‐IPN) membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared for the fuel cell applications. SPI was synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride, 4,4′‐diaminobiphenyl 2,2′‐disulfonic acid, and 2‐bis [4‐(4‐aminophenoxy) phenyl] hexafluoropropane. PEGDA was polymerized in the presence of SPI to synthesize semi‐IPN membranes of different ionic contents. These membranes were characterized by determining, ion exchange capacity, water uptake, water stability, proton conductivity, and thermal stability. The proton conductivity of the membranes increased with increasing PEGDA content in the order of 10^?1 S cm^?1 at 90°C. These interpenetrating network membranes showed higher water stability than the pure acid polyimide membrane. This study shows that semi‐IPN SPI membranes based on PEGDA which gives hydrophilic group and structural stability can be available candidates comparable to Nafion® 117 over 70°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007