混合大二醇基聚氨酯弹性体/环氧树脂互穿网络聚合物的研究

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇作为软链段,首先通过两步溶液聚合法合成了-NCO封端的混合大二醇基聚氨酯(PU)弹性体预聚物(PUT);然后以PUT和环氧树脂(EP)预聚物为原料、1,3-双(γ-氨丙基)-1,1,3,3-四甲基二硅氧烷(BATS)为交联剂,采用同步溶液聚合法合成了PUT/EP互穿聚合物网络(PUT/EP I PN)。使用傅里叶红外光谱(FT-I R)法、动力学分析(DMA)法和扫描电子显微镜(SEM)法,对PUT和PUT/EP I PN进行分析和表征,并对其力学性能和表面疏水性进行测试。实验结果表明,PUT/EP I PN中不存在宏观相分离状态,仅发生微观相分离状态;当PUT/EP I PN中w(PUT)=50%时,PUT/EP I PN具有优异的综合力学性能和表面疏水性。     

A novel approach to interpenetrating networks of epoxy resin and polydimethylsiloxane

A novel methodology for preparing interpenetrating polymer networks (IPNs) between an epoxy resin, diglycidylether of bisphenol A (DGEBA) and polydimethylsiloxane (PDMS) was proposed. The vinyl‐terminated PDMS (vinyl‐PDMS) was partially crosslinked with hydrogen‐containing PDMS (H‐PDMS) and was mixed with DGEBA, modified silica (m‐silica), and a methyl tetrahydrophtalic anhydride (MTHPA) curing agent. Subsequently, the curing reactions of the DGEBA/m‐silica and PDMS were allowed to occur separately and simultaneously leading to an IPN. The m‐silica played a double‐fold role: Cocuring with DGEBA and H‐bonding with the oxygen atoms on the PDMS segments, and thus acted as a compatibilizer between DGEBA and PDMS and promoted the generation of the IPN structure. The resulted partially miscible structure was characterized through the dispersion of silica particles and the glass transition behavior of the samples. The mechanical properties of the IPNs were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

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     

聚氨酯/环氧树脂互穿网络聚合物反应动力学

通过共混法制备了聚氨酯(PU)/环氧树脂(EP)互穿网络聚合物(IPN),采用示差扫描量热法(DSC)和动态机械分析(DMA)对IPN形成过程中的固化反应动力学及产物IPN的相容性进行了研究,结果表明,m(PU)/m(EP)=10∶6的IPN体系的反应级数为0.95,表观活化能为169.23 kJ/mol;PU/EP IPN只有1个玻璃化转变温度,相容性好。     

Synthesis,characterization and properties of organoclay‐modified polyurethane/epoxy interpenetrating polymer network nanocomposites

organoclay‐modified polyurethane/epoxy interpenetrating network nanocomposites (oM‐PU/EP nanocomposites) were prepared by adding organophilic montmorillonite (oMMT) to interpenetrating polymer networks (IPNs) of polyurethane and epoxy resin (PU/EP) which had been prepared by a sequential polymerization technique. Wide‐angle X‐ray diffraction (WAXD) and transmission electronic microscopy (TEM) analysis showed that the interpenetrating process of PU and EP improved the exfoliation and dispersion degree of oMMT. The effects of the NCO/OH ratio (isocyanate index), the weight ratio of PU/EP and oMMT content on the phase structure and the mechanical properties of the oM‐PU/EP nanocomposites were studied by tensile testing and scanning electronic microscopy (SEM). Water absorption tests showed that the PU/EP interpenetrating networks and oMMT had synergistic effects on improvement in the water resistance of the oM‐PU/EP nanocomposites. Differential scanning calorimetry (DSC) analysis showed that PU was compatible with EP and that the glass transition temperature (T_g) of the oM‐PU/EP nanocomposites increased with the oMMT content up to 3 wt%, and then decreased with further increasing oMMT content. The thermal stability of these nanocomposites with various oMMT contents was studied by thermogravimetric analysis (TGA), and the mechanism of thermal stability improvement was discussed according to the experimental results. Copyright © 2005 Society of Chemical Industry     

含有互穿网络结构的丁腈橡胶改性环氧/酚醛胶粘剂的合成及其应用

合成了一种含有互穿网络结构的丁腈橡胶(BN)改性环氧/酚醛胶粘剂。通过扫描电镜(SEM)分析, 证明了此胶片具有互穿网络结构。同时对胶粘剂进行了差热分析(DTA),并考察了其粘结性能以及贮存性能。最后将其成功地应用到一种厚铜箔(0.4～0.5mm)环氧玻璃布层压板上,得到的覆铜板样品具有剥离强度高、平整度好、电性能优良等特点。     

Reinforcement of polyurethane/epoxy interpenetrating network nanocomposites with an organically modified palygorskite

An organophilic palygorskite (o‐PGS) prepared by the treatment of natural palygorskite with hexadecyl trimethyl ammonium bromide was incorporated into interpenetrating polymer networks (IPNs) of polyurethane (PU) and epoxy resin (EP), and a series of PU/EP/clay nanocomposites were obtained by a sequential polymeric technique and compression‐molding method. X‐ray diffraction and scanning electron microscopy analysis showed that adding nanosize o‐PGS could promote the compatibility and phase structure of PU/EP IPN matrices. Tensile testing and thermal analysis proved that the mechanical and thermal properties of the PU/EP IPN nanocomposites were superior to those of the pure PU/EP IPN. This was attributed to the special fibrillar structure of palygorskite and the synergistic effect between o‐PGS and the IPN matrices. In addition, the swelling behavior studies indicated that the crosslink density of PU/EP IPN gradually increased with increasing o‐PGS content. The reason may be that o‐PGS made the chains more rigid and dense. As for the flame retardancy, the PU/EP nanocomposites had a higher limiting oxygen index than the pure PU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison of the pervaporation separation of a water–acetonitrile mixture with zeolite‐filled sodium alginate and poly(vinyl alcohol)–polyaniline semi‐interpenetrating polymer network membranes

The pervaporation (PV) separation performance of ZSM‐5‐ and Na‐Y‐type zeolite‐filled sodium alginate (NaAlg) membranes were compared with those of pure NaAlg and semi‐interpenetrating polymer network (semi‐IPN) membranes of poly(vinyl alcohol) (PVA) with polyaniline (PANI) for the dehydration of acetonitrile. The PV separation characteristics of the zeolite‐filled membranes showed a dependence on the nature of the zeolites. The variation of the acidity function of the ZSM‐5 zeolite had an influence on the flux and selectivity of the membranes when compared to unfilled membranes. The crosslinked membranes were characterized by differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. Increasing the PANI content of the semi‐IPN network increased the separation selectivity. Among the NaAlg membranes, the plain NaAlg membrane showed the highest selectivity of 414 at 30 mass % water in the feed mixture, whereas the Na‐Y‐ and ZSM‐5 (40)‐filled NaAlg membranes exhibited much lower values of selectivity, that is, 7.3 and 4.3, respectively for 30 mass % water in the feed. When the flux and selectivity data of ZSM‐5 (250)‐filled NaAlg membranes were compared with that of Na‐Y‐ or ZSM‐5 (40)‐filled NaAlg membranes, a noticeable increase in the selectivity for the ZSM‐5 (250)‐filled NaAlg membrane was observed, but a somewhat comparable flux was observed compared to the plain NaAlg membrane. For the first time, PANI was polymerized with PVA to yield a semi‐IPN. The total flux and water flux increased systematically, whereas the selectivity decreased greatly from 251.87 to 5.95 with increasing amounts of water in the feed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1968–1978, 2005     

Structure and properties of amine‐hardened epoxy/benzoxazine hybrids: Effect of epoxy resin functionality

Bifunctional, trifunctional, and tetrafunctional epoxy resins (EP) were hardened with stoichiometric amount of 4,4′‐diaminodiphenyl methane in presence and absence of benzoxazine (BOX). The EP/BOX ratio of the hybrid systems was 100/0, 75/25, 50/50, and 25/75 wt %, respectively. Information on the structure of the hybrid systems was received from differential scanning calorimetry, dynamic‐mechanical thermal analysis, atomic force microscopy, and fractographic studies. The flexural and fracture mechanical properties of the EP/BOX hybrids were determined and compared to those of the reference EPs. The thermal degradation and fire resistance of the hybrids were also studied. It was found that the polymerized BOX was built in the network in from of nanoscale inclusions and acted as antiplasticizer. Incorporation of BOX enhanced the flexural modulus and strength and reduced the glass transition temperature of the parent EP. The fracture toughness and energy were practically not improved by hybridization with BOX. The charring and flame resistance were improved with increasing amount of BOX in the EP/BOX hybrids. The relative improvement in the latter was most prominent for the bifunctional EP/BOX systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006     

Effect of the synthesis route on the structure and properties of polyurethane/nitrokonjac glucomannan semi‐interpenetrating polymer networks

With a synthesis route differing from previous methods, novel semi‐interpenetrating polymer networks (semi‐IPNs), coded UNK‐II, were synthesized by the initial mixing of nitrokonjac glucomannan (NKGM) with castor oil in butanone and the subsequent addition of toluene diisocyanate (TDI) to begin the polymerization reaction in the presence of 1,4‐butanediol (BD) as a chain extender at 60°C. The results from dynamic mechanical analysis, differential scanning calorimetry, and ultraviolet spectroscopy indicated that a certain degree of microphase separation occurred between soft and hard segments of polyurethane (PU) in the UNK‐II sheets. The α‐transition temperature, glass‐transition temperature, heating capacity, and tensile strength increased with an increase in the NKGM content, and this suggested an interaction between PU and NKGM in the UNK‐II sheets. In a previous method, semi‐IPN materials (PUNK) were synthesized by the polymerization reaction between castor oil and TDI, and then this PU prepolymer was mixed with NKGM and cured in the presence of BD as a chain extender. The PUNK sheets had relatively good miscibility and mechanical properties. However, for UNK‐II sheets prepared by the method reported in this work, NKGM mainly played a role in reinforcement. When the NKGM content was less than 10%, the UNK‐II sheets exhibited good miscibility, tensile strength (26–28 MPa), and breaking elongation (130–140%), similar to those of PUNK materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1948–1954, 2003     

Temperature and pH‐response swelling behavior of poly(2‐ethyl‐2‐oxazoline)/chitosan interpenetrating polymer network hydrogels

Interpenetrating polymer network (IPN) hydrogels composed of poly(2‐ethyl‐2‐oxazoline) (PEtOz) and chitosan (CS) were prepared with radical polymerization and were characterized for their swelling properties. Sample OC11 (hydrogel weight ratio PEtOz/CS = 1/1) swelled more than samples OC21 (PEtOz/CS = 2/1) and OC31 (PEtOz/CS =3/1), exhibiting a swelling ratio of about 2000 wt % in deionized water; the swelling ratios of the other samples were about 1000 and 700 wt %. The swelling behavior of the IPN hydrogels was observed under various pH and temperature conditions. The swelling ratios of the samples ranged from about 2000 to 6500 wt % at lower pHs, with a maximum swelling ratio of about 6500 wt % in a pH 2 aqueous solution. They exhibited low critical solution temperature behavior, with sample OC31 more sensitive to temperature and sample OC11 more sensitive to pH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1100–1103, 2006     

Preparation of SBS/poly(styrene–methyl methacrylate) thermoplastic interpenetrating polymer network

SBS as polymer I, poly(styrene–methyl methacrylate) polymerized by atom transfer radical polymerization as polymer II, and a thermoplastic interpenetrating polymer network of SBS/poly(styrene–methyl methacrylate) were prepared by the sequential method. The effects of the polymerization temperature, the composition of the catalyst, the ratio of the monomers studied, and the kinetics at 90°C were also investigated. It was shown that when polymerization was initiated by a BPO/CuCl/bpy (BPO:CuCl:bpy = 1:1:3) system at 90°C, the mass averaged molecular weight of the poly(styrene–methyl methacrylate) increased with monomer conversion, and the polydispersities were kept very low. Fourier transform infrared spectroscopy and gel permeation chromatogram showed that poly(styrene–methyl methacrylate) with low polydispersities had been synthesized. Thus, a thermoplastic interpenetrating polymer network comprised of both narrow molecular‐weight‐distribution components was successfully prepared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2007–2011, 2003     

Fabrication of interpenetrating polymer network to enhance the biological activity of synthetic hydrogels

A three dimensional porous hydrogel with suitable biological and mechanical properties are required for bone tissue engineering. Hydrogels of poly(lactic-ethylene oxide fumarate) (PLEOF), crosslinked with poly(ethylene glycol)-diacrylate (PEG-da) have desirable mechanical properties, however, their application for bone regeneration is limited due to the lack of cell motif sites within their structure. The aim of this study was to incorporate a naturally derived polymer such as gelatin into PLEOF hydrogels to promote their biological properties. Interpenetrating polymer network (IPN) was used as an efficient technique to acquire uniform mixture of these two polymers. Additionally gas foaming agents were used to create pores with average diameter of 250 μm in these IPN hydrogels. The concentrations of PEG-da and gelatin were optimized to tune the mechanical strength and degradation properties of these hydrogels. A compression modulus of 500 kPa was achieved for hydrogel fabricated with 400 mg/ml PLEOF, 200 mg/ml PEG-da and 150 mg/ml gelatin. The addition of gelatin to PLEOF elevated the compression modulus by two-fold and decreased the energy loss by 40%. The result of protein analysis demonstrated that IPN substantially enhanced the retention of physically crosslinked gelatin in the 3D structure of hydrogel. More than 50% of gelatin was retained in IPN hydrogel after two weeks of incubation in simulated physiological environment. Preserving gelatin in the hydrogel structure provides cell motif sites for a longer period of time, which is desirable for uniform cell proliferation. In vitro studies showed that primary human osteoblast cells adhered and proliferated in PLEOF-gelatin hydrogel. These results demonstrated the potential of using this IPN hydrogel for bone tissue engineering.     

Synthesis and properties of elastomer‐modified epoxy–methacrylate sequential interpenetrating networks

The structure and properties of copolymerized sequential‐interpenetrating networks (SeqIPNs) synthesized from amine‐cured epoxies and free‐radical polymerized dimethacrylates were examined. Materials were synthesized with and without the incorporation of an epoxy‐terminated butadiene–nitrile reactive elastomer. Synthesis proceeded through full thermal cure of the epoxy–amine network, followed by polymerization of the methacrylate network. The methacrylate reactions were free‐radically induced using thermal (peroxide‐initiated) or photochemical [electron‐beam (e‐beam)] techniques. Fourier transform infrared spectroscopy was used to monitor epoxy–amine step‐growth polymerization in situ and to measure final cure conversion of methacrylates. Structural examination of the IPNs using atomic force microscopy and scanning electron microscopy revealed microphase separation in the neat–SeqIPN materials and macroscopic phase separation of rubber‐rich domains for elastomer‐modified networks. Dynamic mechanical analysis of the SeqIPN determined that the properties of the network are strongly dependent on the cure conditions. Furthermore, the viscoelastic behavior of the e‐beam–cured SeqIPN could be adequately described by the Williams–Landel–Ferry and Kohrausch–Willams–Watts equations, presumably because of a strong coupling between the epoxy–amine and methacrylate networks. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 530–545, 2001     

环氧树脂增韧改性新技术

详细介绍了环氧树脂增韧改性新技术———互穿网络结构 (IPN)、柔性链段固化剂和热致液晶聚合物 (TLCP)增韧环氧树脂的发展现状 ,并对增韧机理作了简单的概述     

Morphology and thermal and dielectric behavior of cycloaliphatic epoxy/trimethacrylate interpenetrating polymer networks for vacuum‐pressure‐impregnation electrical insulation

Vacuum pressure impregnation has been known as the most advanced impregnation technology that has ever been developed for large and medium high‐voltage electric machines and apparatuses. We developed one new type of vacuum‐pressure‐impregnation resin with excellent properties by means of a novel approach based on in situ sequential interpenetrating polymer networks resulting from the curing of trimethacrylate monomer [trimethylol‐1,1,1‐propane trimethacrylate (TMPTMA)] and cycloaliphatic epoxy resin (CER). In this study, the influence of the concentrations of the components and their microstructures on their thermal and dielectric behaviors were investigated for the cured CER/TMPTMA systems via atomic force microscopy, dynamic mechanical analysis, thermogravimetric analysis, and dielectric analysis. The investigation results show that the addition of TMPTMA to the CER–anhydride system resulted in the formation of a uniform and compact microstructure in the cured epoxy system. This led the cured CER/TMPTMA systems to show much higher moduli in comparison with the pure CER–anhydride system. The thermogravimetric analysis results show that there existed a decreasing tendency in the maximum thermal decomposition rates of the cured CER/TMPTMA systems, which implies that the thermal stability properties improved to some extent. The dielectric analysis results show that the cured CER/TMPTMA systems displayed quite different dielectric behaviors in the wide frequency range 0.01 Hz–1 MHz and in the wide temperature range 27–250°C compared with the cured CER–anhydride system. © 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     

Property evaluation and structure analysis of polyurethane/epoxy graft interpenetrating polymer networks

Polyurethanes obtained from 4,4′‐diphenylmethane diisocyanate (MDI) and polydiols with different molecular weights (polyethylene glycol and polyoxypropylene diols) were used as modifiers for diglycidyl ether of bisphenol A. Impact strength (IS), critical stress intensity factor (K_C), flexural strength and flexural strain at break were measured as a function of polyurethane (PUR) type and content. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared spectroscopy (FTIR) were employed for the structure and morphology analysis. It was found that the addition of polyurethane with an excess of isocyanate groups to epoxy resin resulted in the formation of a grafted interpenetrating polymer network structure. The mechanical properties of epoxy resin were improved with 5 and 10% PUR. Moreover, it was observed that composites containing PUR based on higher molecular weight (PUR 1002 and PUR 2002) with long flexible segments exhibited higher impact strength while PUR prepared from polyethylene glycol had a higher flexural energy to break and a higher flexural modulus. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011