热固性环氧树脂改性沥青粘结剂的性能研究

以环氧树脂为沥青改性剂制备了热固性环氧沥青粘结剂。利用示差扫描量热仪(DSC)、动态热力学分析(DMA)、万能材料试验机和布氏旋转粘度计研究了环氧树脂改性沥青粘结剂的等温和非等温固化反应、玻璃化转变温度(Tg)、阻尼行为、力学性能和粘温特性。结果表明,环氧沥青粘结剂等温固化反应属于自催化反应,沥青的加入大大地降低了环氧树脂的固化热,其固化后只有1个Tg(远高于纯沥青的Tg),说明环氧树脂和沥青有很好的相容性。环氧沥青粘结剂还具有优异的阻尼行为,很高的拉伸强度和韧性。     

The swelling behaviors and network parameters of cationic starch‐g‐acrylic acid/poly(dimethyldiallylammonium chloride) semi‐interpenetrating polymer networks hydrogels

Amphiphilic semi‐interpenetrating polymer networks (semi‐IPN) hydrogels were prepared by a sequential‐IPN method by acrylic acid graft copolymerization into cationic starch in mild aqueous media of poly(dimethyldiallylammonium chloride). Some main factors were investigated to evaluate the swelling of hydrogels, and the network parameters M_c were given accordingly to elaborate the interaction between polymers. The chemical structure of the resulting hydrogel was confirmed using Fourier transform infrared spectroscopy. The cationic starch‐based semi‐IPN hydrogels achieved a high swelling capacity of 1070 g/g in deionized water and 94 g/g in 0.9 wt % NaCl solution, respectively) and high compressive stress in a high water content. Besides, a different pH‐dependent behavior was found for this semi‐IPN hydrogel. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(vinyl acetate)/polyacrylate semi‐interpenetrating polymer networks. II. Thermal,mechanical, and morphological characterization

The thermal, dynamic mechanical, and mechanical properties and morphology of two series of semi‐interpenetrating polymer networks (s‐IPNs) based on linear poly(vinyl acetate) (PVAc) and a crosslinked n‐butyl acrylate/1,6‐hexanediol diacrylate copolymer were investigated. The s‐IPN composition was varied with different monoacrylate/diacrylate monomer ratios and PVAc concentrations. The crosslinking density deeply affected the thermal behavior. The results showed that a more densely crosslinked acrylate network promoted phase mixing and a more homogeneous structure. The variation in the linear polymer concentration influenced both the morphology and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal,mechanical properties,and low‐temperature performance of fibrous nanoclay‐reinforced epoxy asphalt composites and their concretes

Epoxy asphalt (EA) concretes have been widely used in the pavement of orthotropic steel bridge decks. The objective of this study was to figure out the enhanced effects of natural fibrous attapulgite (ATT) as a reinforced nanofiller in ATT/EA nanocomposites through a comparison of the properties of the composites with a series of various nanoclay loadings. The rheological properties, glass transition, thermal stability, mechanical properties, and morphology of the ATT/EA composites were characterized. Furthermore, the low‐temperature flexibility of the ATT/EA concretes was investigated. The test results show that the addition of ATT had no significant effect on the rotational viscosity of EA in the initial stage of the curing reaction. In addition, the ATT/EA composites showed better performance than the neat one in thermal stability with a higher glass‐transformation temperature. The tensile strength and elongation at break of the ATT/EA composites at a loading of 0.5 wt % ATT were 21 and 22% higher than those of the neat EA. The addition of ATTs also enhanced the low‐temperature flexibility of the EA concretes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41694.     

Structure–property relationships in acrylate/epoxy interpenetrating polymer networks: Effects of the reaction sequence and composition

Interpenetrating polymer networks (IPNs) of poly(ethylene glycol) 200 diacrylate and diglycidyl ether of bisphenol A were formed over a range of compositions and with different reaction sequences. We controlled the reaction sequence by thermally initiating the cationic epoxy polymerization, photoinitiating the free‐radical acrylate polymerization, and changing the processing order. The reaction was monitored by attenuated total reflectance Fourier transform infrared spectroscopy, photo differential scanning calorimetry. and modulated differential scanning calorimetry (mDSC). The glass‐transition temperature was estimated from mDSC. Mechanical and rheological tests provided the strength and hardness of the materials. Morphology and phase separation were explored with optical and scanning electron microscopy. All of the physical properties were dependent on IPN composition. Some properties and the morphology were dependent on the reaction sequence. Significant differences in glass‐transition temperature were observed at the same composition but with different reaction sequences. Even with minimal structure, correlations existed between the morphology and material properties with partially phase‐separated samples exhibiting maximum damping. The rapid reaction allowed minimal phase separation, yet different reaction sequences resulted in significantly different properties. This systematic study indicated that the relationships between phase morphology, processing, and the physical properties of IPNs are complex and not predictable a priori. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 891–901, 2007     

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     

Improved shape memory effects in multiwalled‐carbon‐nano‐tube reinforced thermosetting polyurethane composites

Shape memory thermosetting polyurethane (SMPU) composites containing different amount of multiwalled carbon nanotube (MWCNT) ranging from 0 to 0.250 phr were prepared. The shape memory behavior, tensile stress, and recovery stress were determined by using conventional thermomechanical cycle; however, the modified thermomechanical cycle designated as progressive stretch–relax–stretch (PSRS) cycle was also employed to create shape memory effects in studied composites. The test was carried out in water bath which was equipped with an electric heater, temperature controller, and tensile stress and strain measuring setup. The recovery and tensile stresses both were showing higher values for PSRS samples as compared with conventional samples. Loading of MWCNT improved the recovery stress of SMPU, thereby confirming reinforcing effect. The maximum recovery stress of 2.17 MPa for 0.188 phr MWCNT loading was observed as compared with 1.09 MPa of unreinforced SMPU specimen. The recovery time was also improved on reinforcement as demonstrated in this article. The morphology of fractured surface and degree of dispersion of MWCNT was studied using Field Emission Scanning Electron Microscope. The impact on glass transition temperature was also observed for MWCNT reinforcement on SMPU, which depends on the degree of dispersion and loading of MWCNT in the specimen. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44389.     

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     

Synthesis and swelling properties of pH‐ and temperature‐sensitive interpenetrating polymer networks composed of polyacrylamide and poly(γ‐glutamic acid)

Novel hydrogels of interpenetrating polymer networks (IPNs) composed of polyacrylamide and poly(γ‐glutamic acid) were synthesized. In these systems, both polymers were crosslinked independently; this reduced the potential loss of a polymer during the washing process, as often occurs in semi‐IPN systems. Interpolymer interactions were investigated with Fourier transform infrared spectroscopy and differential scanning calorimetry. These studies suggested possible interactions between both polymers by the formation of hydrogen bonds. The swelling behavior of these hydrogels was analyzed by immersion of the hydrogel samples in deionized water at 25 and 37°C and in buffer solutions with pHs of 3, 7, and 10. The kinetics of swelling showed increases in the values of the swelling ratio with increasing immersion time in the swelling medium, molar proportion of the biopolymer in the hydrogel, temperature, and pH of the swelling medium. All of the hydrogels swelled rapidly and reached equilibrium in an average time of 40 min. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Mechanical properties of blocked polyurethane/epoxy interpenetrating polymer networks

The mechanical properties of blocked polyurethane(PU)/epoxy interpenetrating polymer networks (IPNs) were studied by means of their static and damping properties. The studies of static mechanical properties of IPNs are based on tensile properties, flexural properties, hardness, and impact method. Results show that the tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs decreased with increase in blocked PU content. The impact strength of IPNs increased with increase in blocked PU content. It shows that the tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (CaCO₃) content to a maximum value at 5, 10, 20, and 25 phr, respectively, and then decreased. The higher the filler content, the greater the hardness of IPNs and the lower the notched Izod impact strength of IPNs. The glass transition temperatures (T_g) of IPNs were shifted inwardly compared with those of blocked PU and epoxy, which indicated that the blocked PU/epoxy IPNs showed excellent compatibility. Meanwhile, the T_g was shifted to a higher temperature with increasing filler (CaCO₃) content. The dynamic storage modulus (E′) of IPNs increased with increase in epoxy and filler content. The higher the blocked PU content, the greater the swelling ratio of IPNs and the lower the density of IPNs. The higher the filler (CaCO₃) content, the greater the density of IPNs, and the lower the swelling ratio of IPNs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1826–1832, 2006     

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     

Synthesis and properties of the semi‐interpenetrating polymer network–like,thermosensitive poly(N‐isopropylacrylamide) hydrogel

A new strategy was used to prepare a semi‐interpenetrating polymer network (semi‐IPN)–like poly(N‐isopropylacrylamide) (PNIPAAm) polymeric hydrogel, consisting of either low (2300) or high (33,000) molecular weight linear PNIPAAm chains and the crosslinked PNIPAAm network. The properties of the resulting PNIPAAm hydrogels were characterized by DSC and SEM as well as their swelling ratios at various temperatures, the deswelling in hot water (48°C), and the oscillating shrinking–swelling properties within small temperature cycles. It was found that the deswelling rate of these semi‐IPN–like PNIPAAm hydrogels was improved if the molecular weight and/or composition of the linear PNIPAAm chains within the semi‐IPN–like PNIPAAm hydrogels were increased. This improved deswelling rate was attributed to the fast response nature of the linear PNIPAAm chains and the increased pore number in the matrix network, which provided numerous water channels for the water to diffuse out during the deswelling process at a temperature above the lower critical solution temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1935–1941, 2003     

Modification of epoxy asphalt by low-doping PE-GMA and PE-MAH

Low-density polyethylene grafted glycidyl methacrylate (PE-GMA) and low-density polyethylene maleic anhydride (PE-MAH) are low-cost commercialized polymeric materials. Because of their low viscosity, molecular flexibility, solubility parameters, and polarity similar to asphalt or epoxy resins, PE-GMA and PE-MAH are added to epoxy asphalt (EA) to improve the compatibility and toughness of EA. The microstructure, viscosity, thermal stability, dynamic mechanical behavior, and mechanical properties of PE-GMA and PE-MAH modified EA were investigated. Smaller and more uniformly distributed asphalt particles were formed in mixes with lower PE-GMA or PE-MAH content. The polymer dispersity index of the modified EA is 1.1–1.4 lower than that of the pure EA, and compatibility is significantly improved. The reason is that PE-GMA and PE-MAH are polyethylene with polar functional groups, and their molecular structure includes both polar functional groups and nonpolar polyethylene chains, improving the compatibility between polar epoxy resin and nonpolar asphalt in EA. In addition, the incorporation of PE-GMA or PE-MAH effectively improves the low-temperature toughness of EA. It also has high damping performance and tan δ, improved the durability and comfort of EA pavement.     

Effects of different interphases on the mechanical properties of cured silanized silica‐filled styrene–butadiene/polybutadiene rubber blends for use in passenger car tire treads

Polybutadiene (BR) and styrene–butadiene (SBR) rubbers containing the same loading of precipitated silica nanofiller were prepared. The silica surfaces were pretreated with bis(3‐triethoxysilylpropyl) tetrasulfide to chemically bond the silica to the rubber. The rubber compounds were mixed together for different times and at different temperatures to produce SBR/BR blends. The mass fraction and composition values of the interphases in the blends were subsequently determined with modulated‐temperature differential scanning calorimetry. These properties changed substantially as a function of mixing temperature and mixing time. The hardness, tensile strength, elongation at break, stored energy density at break, tear strength, modulus, abrasion resistance, heat buildup, and loss tangent of the cured blends were measured over a wide range of test conditions. Elongation at break, stored energy density at break, tearing energy, and abrasion resistance benefited from increases in the mass fraction of the interphase. The remaining properties were influenced mainly by the filler loading and mixing time of the two rubber compounds. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Layer‐by‐layer fabrication of nacre inspired epoxy/MMT multilayered composites

The organic–inorganic hybrid multilayered composites are prepared using a unique combination of poly[(o‐cresyl glycidyl ether)‐co‐formaldehyde] (CNER), amino modified montmorillonite (NH₂‐MMT), and polyethyleneimine (PEI). This tricomponent composite multilayer PEI(CNER/NH₂‐MMT/PEI)_n deposited via layer ‐ by ‐ layer technique is based upon synergistic combination of covalent and hydrogen bonding. The growth of multilayer was monitored using UV–vis spectroscopy and ellipsometry. When subjected to optical analyses, the prepared multilayered composite films revealed profound optical transmittance ～83%–87%. The surface morphological analysis by atomic force microscopy and scanning electron microscopy revealed uniform arrangement of organic–inorganic components with relative increase in intensity of elements (C, N, O, Si) as confirmed by X‐ray photoelectron spectroscopy studies. The multilayered composites possess 1.99 GPa hardness making them potential candidate for a number of applications where mechanical strength is desired. Moreover, significant resistance against alkaline and organic solvents at minimal deterioration of circa 0.12% has also been observed for the prepared films. The epoxy clay based thin films being robust, scratch resistant, hydrophilic, chemically inert, and mechanically strong are potential candidates for advanced environmental applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46079.     

Polyurethane–epoxy maleate of bisphenol a semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks were synthesized starting from polyurethane (PU) and epoxy maleate of bisphenol A (EMBA). Differential scanning calorimetry and swelling measurements showed good miscibility and the presence of the strong intermolecular interactions within the synthesized networks. The physicomechanical properties increased against PU to a maximum value with the increasing of EMBA content up to 12 wt % and then decreased with further increasing EMBA content. Generally, with exception of the elongation at the limit of elasticity, the mechanical properties improved very much under action of the UV radiation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 138–144, 2002     

Synthesis and mechanical properties of leather–epoxy interpenetrating polymer networks

Leather–epoxy interpenetrating polymer networks (IPNs) were synthesized; these IPNs have an approximate epoxy concentration of 25 wt %. The flexural and tensile moduli of the IPNs prepared are equivalent to those of the epoxy resin. The Izod impact energy and fracture toughness measured for the IPNs, however, exceed those attained by the epoxy resin alone by at least a factor of 4. The glass transition of leather–epoxy IPNs occurs over a wide temperature range, thus indicating that the IPN is an intimate admixture of the epoxy resin throughout the collagen matrix of the hide. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1224–1232, 2000     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (T_g) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three T_g values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003     

Amine/epoxy stoichiometric ratio dependence of crosslinked structure and ductility in amine-cured epoxy thermosetting resins

Epoxy-amine thermosetting resins undergo different reactions depending on the amine/epoxy stoichiometric ratio (r). Although many desirable properties can be achieved by varying the stoichiometric ratio, the effects of the variation on the crosslinked structure and mechanical properties and the contribution of these factors to the ductility of materials have not been fully elucidated. This study investigates the brittle-ductile behavior of epoxies with various stoichiometric ratios and performs curing simulations using molecular dynamics (MD) to evaluate the crosslinked structures. The molecular structure is predominantly branched in low-stoichiometric ratio samples, whereas the chain extension type structure dominates the high-stoichiometric ratio samples. As a result, the higher-stoichiometric ratio samples enhances the ductility of materials and the elongation at break increases form 1.4% (r = 0.6) to 11.4% (r = 1.4). Additionally, the tensile strength (105.4 MPa) and strain energy (7.96 J/cm³) are maximum at r = 0.8 and 1.2, respectively. On the other hand, the Young's modulus is negatively impacted and it decreased from 4.2 to 2.7 GPa with increasing stoichiometric ratio.