糠醇缩水甘油醚稀释的环氧体系的性能研究

通过力学性能和热性能测试研究了糠醇缩水甘油醚(FGE)稀释的双酚A环氧树脂(DGEBA)体系的固化性能和固化反应动力学。通过Málek自催化机理模型求得添加10%FGE的DGEBA与脂肪族聚酰胺固化剂的固化反应平均活化能为64.66kJ/mol,低于苄基缩水甘油醚(BGE)稀释体系。以FGE稀释的固化产物的拉伸强度达到62.93MPa,比BGE体系高出20%左右。拉伸伸长率达4.66%,是BGE体系的4倍左右。添加FGE的固化物冲击强度达36.17MPa,比BGE体系高出约70%左右。使用FGE和BGE的环氧固化物的玻璃化转变温度分别为46.32℃和52.36℃。FGE和BGE体系固化物的5%的热失重温度分别为260.79℃和194.59℃。FGE是1种良好的环氧树脂稀释剂。     

Optimization of thermal remendability of epoxy via blending

To prepare epoxy materials with improved thermal remendability, two types of epoxy resins (N,N-diglycidyl-furfurylamine (DGFA) and furfuryl glycidyl ether (FGE)), which were synthesized in the authors' lab and contained different proportions of furan and epoxide groups, were blended and cured by anhydride and maleimide. Like the cured version of either DGFA or FGE alone, the cured blends of DGFA and FGE have also acquired thermal reversibility due to the Diels-Alder (DA) bonds from the reaction between furan and maleimide groups. The addition of FGE into the blends increased the DA bonds density as a result of the higher furan concentration in FGE. Accordingly, remendability originating from successive retro-DA and DA reactions was obviously improved. On the other hand, the crosslinked epoxy networks generated by the reaction between epoxide and anhydride groups were strong enough to provide the blends with acceptable mechanical performance.     

Modification of epoxy resins with poly(aryl ether ketone)s

Poly(aryl ether ketone)s were used as modifiers for bisphenol-A diglycidyl ether epoxy resin (AER 331) cured with methyl hexahydrophthalic anhydride. Poly(phthaloyl diphenyl ether) (PPDE), soluble in the uncured epoxy resin without using solvents, was prepared by the Friedel-Crafts reaction of phthaloyl chloride and diphenyl ether. The mechanical, thermal, and dynamic viscoelastic properties of the modified resins with PPDE were examined and compared to the parent resin (AER 331). The fracture toughness, K_IC, for the modified resins increased at no expense to their mechanical and thermal properties on 10 wt % addition of PPDE with molecular weights of more than 17,000. The toughening mechanism is discussed based on the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system.     

Synthesis and properties of fluorinated biphenyl‐type epoxy resin

A novel fluorinated biphenyl‐type epoxy resin (FBE) was synthesized by epoxidation of a fluorinated biphenyl‐type phenolic resin, which was prepared by the condensation of 3‐trifluoromethylphenol and 4,4′‐bismethoxymethylbiphenyl catalyzed in the presence of strong Lewis acid. Resin blends mixed by FBE with phenolic resin as curing agent showed low melt viscosity (1.3–2.5 Pa s) at 120–122°C. Experimental results indicated that the cured fluorinated epoxy resins possess good thermal stability with 5% weight loss under 409–415°C, high glass‐transition temperature of 139–151°C (determined by dynamic mechanical analysis), and outstanding mechanical properties with flexural strength of 117–121 MPa as well as tensile strength of 71–72 MPa. The thermally cured fluorinated biphenyl‐type epoxy resin also showed good electrical insulation properties with volume resistivity of 0.5–0.8 × 10¹⁷ Ω cm and surface resistivity of 0.8–4.6 × 10¹⁶ Ω. The measured dielectric constants at 1 MHz were in the range of 3.8–4.1 and the measured dielectric dissipation factors (tan δ) were in the range of 3.6–3.8 × 10^?3. It was found that the fluorinated epoxy resins have improved dielectric properties, lower moisture adsorption, as well as better flame‐retardant properties compared with the corresponding commercial biphenyl‐type epoxy resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

双马来酰亚树脂基体的湿热特性研究

本文以四官能环氧树脂基体作参比物、选择两种典型的双马来酰亚胺树脂基体（环氧改性双马基体、烯丙基双酚Ａ／双马共聚基体）作为对象，研究其吸湿特性以及吸湿对树脂基体性能的影响，结果表明，树脂基体的化学结构和交联密度对吸湿特性有较大的影响，吸湿量对树脂基体性能的影响也与基体材料的类型，交联密度有关，不能简单地用给定时间下的吸湿率来评定树脂基体的湿热性能优劣。     

Toughened cycloaliphatic epoxy resin for demanding thermal applications and surface coatings

An epoxy resin based on nonglycidyl ether and varying content of carboxyl‐terminated (poly)butadiene acrylonitrile copolymer was cured using an aromatic amine hardener. The ultimate aim of the study was to modify the brittle epoxy matrix by the liquid rubber to improve toughness characteristics. Fourier transform infrared spectroscopic analysis of the modified was performed to understand the structural transformations taking place during the uncured and cured stage of the modified systems. The decreasing trend in exothermal heat of reaction with increasing rubber content in the epoxy resin can be explained by the fact that the increase of carboxyl‐terminated butadiene acrylonitrile copolymer (CTBN) modifier might induce a high reactivity of the end groups with the epoxide ring and resulting shorter curing times and, hence, the faster curing process than the unmodified resin. Tensile strength, impact strength, and elongation‐at‐break behaviors of neat as well as modified networks have been studied to observe the effect of rubber modification. Blends sample exhibits better properties as compared to pure epoxy resin in terms of increase in impact strength and elongation‐at‐break of the casting and gloss, scratch hardness, adhesion, and flexibility of the film. The improvement in these properties indicate that the rubber‐modified resin would be more durable than the epoxy based on di glycidyl ether of bis‐phenol‐A and other epoxies. The films of coating based on epoxy with 15 wt % CTBN offered the maximum resistance toward different concentrations of acids, alkalies, and solvents as compared to the cured films of other blend samples. The thermal stability of the cycloaliphatic‐based epoxy resin was increased with the addition of 15 wt % CTBN in epoxy matrix. Cycloaliphatic‐based epoxy network modified with CTBN displayed two phase separated morphology with dispersed rubber globules in the matrix resin, i.e., they revealed the presence of two phase morphological features. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

Epoxy resins based on resorcinol and its derivatives

Schemes are presented for the synthesis of epoxy oligomers based on resorcinol and its derivatives. The properties of furfurylresorcinol glycidyl ethers (UP-63 resin), oligomeric glycidyl ethers of glycerol dihydroxydiphenyl ether (UP-67 resin), diglycidyl ether of ethylene glycol dihydroxydiphenyl ether (UP-622 resin), and oligomeric glycidyl ether of pentaerythritol and resorcinol (UP-635 resin) are considered. These resins are shown to be substantially advantageous compared to standard bisphenol A-based epoxy oligomers. Materials possessing higher thermal stability and adhesion are developed on their basis.     

Properties of a reactive‐graphitic‐carbon‐nanofibers‐reinforced epoxy

Our previous studies showed that herringbone graphitic GNFs surface‐derivatized with reactive linker molecules bearing pendant primary amino functional groups capable of binding covalently to epoxy resins. Of special importance, herringbone GNFs derivatized with 3,4′‐oxydianiline (GNF‐ODA) were found to react with neat butyl glycidyl ether to form mono‐, di‐, tri‐, and tetra‐glycidyl oligomers covalently coupled to the ODA pendant amino group. The resulting reactive GNF‐ODA (butyl glycidyl)_n nanofibers, r‐GNF‐ODA, are especially well suited for reactive, covalent incorporation into epoxy resins during thermal curing. Based on these studies, nanocomposites reinforced by the r‐GNF‐ODA nanofibers at nanofiber loadings of 0.15–1.3 wt% were prepared. Flexural property of cured r‐GNF‐ODA/epoxy nanocomposites were measured through three‐point‐bending tests. Thermal properties, including glass transition temperature (T_g) and coefficient of thermal expansion (CTE) for the nanocomposites, were investigated using thermal mechanical analysis. The nanocomposites containing 0.3 wt% of the nanofibers gives the highest mechanical properties. At this 0.3‐wt% fiber loading, the flexural strength, modulus and breaking strain of the particular nanocomposite are increased by about 26, 20, and 30%, respectively, compared to that of pure epoxy matrix. Moreover, the T_g value is the highest for this nanocomposite, 14°C higher than that of pure epoxy. The almost constant change in CTEs before and after T_g, and very close to the change of pure epoxy, is in agreement with our previous study results on a chemical bond existing between the r‐GNF‐ODA nanofibers and epoxy resin in the resulting nanocomposites. POLYM. COMPOS., 28:605–611, 2007. © 2007 Society of Plastics Engineers     

Synthesis of naphthalene containing aralkyl novolac epoxy resins for electronic application

Naphthalene containing aralkyl novolac epoxy resins were synthesized by the condensation of p‐xylylene glycol with 2,7‐dihydroxynaphthalene or 2‐naphthol followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. Comparisons of mono‐ and di‐functional naphthalene containing aralkyl novolac epoxy resins based on thermal and moisture absorption properties were also studied. The results indicate that a naphthalene containing aralkyl epoxy resin made from the difunctional naphthol has a low coefficient of thermal expansion, high heat resistance, and low moisture absorption.     

Effect of organo‐phosphorus and nano‐clay materials on the thermal and fire performance of epoxy resins

The results of flame retardance and thermal stability of a reactively modified organo‐phosphorus diglycidylether of bisphenol‐A and an organo‐phosphorus tetraglycidyl diaminodiphenylmethane are reported here. The organo‐phosphorus epoxy resins were synthesized by the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and diglycidyl ether of bisphenol‐A and tetraglycidyl diaminodiphenylmethane, respectively, and then cured with a mixture of 3,5‐diethyltoluene‐2,4‐diamine and 3,5‐diethyltoluene‐2,6‐diamine. In addition to this, between 5 and 7.5% of organically modified polymeric layered silicate nano‐clay was also added to neat epoxy resin or to the phosphorus‐modified epoxy resin to investigate any synergies, or otherwise, a combination of clay and phosphorus on the flame, degradation, and thermal properties are also reported. The reaction kinetics of phosphorus‐modified and epoxy cure were studied by FTIR, ¹H‐NMR, and DSC. Thermal properties and morphology of the final product were analyzed by thermogravimetric analysis, dynamic mechanical thermal analysis, X‐ray diffraction, and cone calorimetry. Improvement in flame retardance by cone calorimetry was demonstrated by the addition of only 3% phosphorus or 7.5% clay into the epoxy compared with unmodified epoxy resins, whereas no evidence of synergy for a phosphorus and clay combination was found. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1233–1253, 2004     

Loading the polyol carbonization agent into clay nanotubes for the preparation of environmentally stable UV‐cured epoxy materials

The halloysite nanotubes (HNTs) were loaded with pentaerythritol (PER). The as‐prepared composite (HNT‐P) and ammonium polyphosphate (APP) was subsequently added to the UV‐curable epoxy resins, giving a new flame‐resistant system. Loading of the hydrophilic PER into HNT can reduce the moisture absorption in the UV‐curable epoxy resins. The flame retardancy was evaluated by means of the cone calorimeter and limit oxygen index test. The results showed that the flame retardancy of the modified epoxy resin was greatly improved with an obvious decrease in both the heat release and smoke release. Moreover, it was revealed that HNT could catalyze the reaction of APP and PER, and the burning surface of the epoxy resin should be covered by the polyphosphoric‐HNT intumescent char layer. We have measured the moisture sorption and dynamic mechanical properties of the UV‐cured epoxy resins. As compared to the use of the simple mixture of PER and HNT, the use of the HNT‐P nearly kept the storage modulus at about 1809 Mpa and reduced the moisture absorption by 58.2 wt % at 40 °C. The results proved that the addition of the HNT‐P obtained lower moisture absorption and higher stability of the mechanical properties than adding the simple mixture. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45045.     

Surface modification of epoxy resin with fluorine-containing methacrylic ester copolymers

To improve oil and water repellency, fluorine-containing block copolymers, which were composed of methyl methacrylate (MMA), glycidyl methacrylate (GMA), and 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (PFA), were blended with an epoxy resin. It was expected that a glycidyl group would mesh with the epoxy resin by primary bonding, and the low surface energy fluorocarbon segment would absorb and orient to the exterior to fluorinate the surface. X-ray photoelectron spectroscopy, contact angle, and peel strength of pressure-sensitive adhesives for modified epoxy resin surface were determined. The amount of fluorine obtained via angular-dependent ESCA investigation in the modified resin surfaces increased with the shallowing of the sampling depth. With increasing modifier content, the amount of fluorine in the modified resin surface layer increased, and the critical surface tension of modified resin surfaces and the peel strength of a silicone pressuresensitive adhesive affixed to the modified epoxy resin, decreased. A considerable amount of fluorine in the resin surface modified with GMA-containing block copolymers remained after Soxhlet extraction, whereas in the surface modified with copolymer without GMA, more fluorine was extracted. It was extracted. It was shown that these copolymers were good surface modifiers to improve oil and water repellency. © 1993 John Wiley & Sons, Inc.     

Preparation and properties of high performance phthalide‐containing bismaleimide modified epoxy matrices

A series of intercrosslinked networks formed by diglycidyl ether of bisphenol A epoxy resin (DGEBA) and novel bismaleimide containing phthalide cardo structure (BMIPP), with 4,4′‐diamino diphenyl sulfone (DDS) as hardener, have been investigated in detail. The curing behavior, thermal, mechanical and physical properties and compatibility of the blends were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), notched Izod impact test, scanning electron microscopy (SEM) and water absorption test. DSC investigations showed that the exothermic transition temperature (T_p) of the blend systems shifted slightly to the higher temperature with increasing BMIPP content and there appeared a shoulder on the high‐temperature side of the exothermic peak when BMIPP content was above 15 wt %. TGA and DMA results indicated that the introduction of BMIPP into epoxy resin improved the thermal stability and the storage modulus (G′) in the glassy region while glass transition temperature (T_g) decreased. Compared with the unmodified epoxy resin, there was a moderate increase in the fracture toughness for modified resins and the blend containing 5 wt % of BMIPP had the maximum of impact strength. SEM suggested the formation of homogeneous networks and rougher fracture surface with an increase in BMIPP content. In addition, the equilibrium water uptake of the modified resins was reduced as BMIPP content increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of 3,3′‐bis (maleimidophenyl)phenylphosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices

An intercrosslinked network of polysulfone (PSF)—bismaleimide (BMI) modified epoxy matrix system was made by using diglycidyl ether of bisphenol A (DGEBA) epoxy resin, hydroxyl terminated polysulfone and bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide) with diaminodiphenylmethane (DDM) as curing agent. BMI–PSF–epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, flexural strength, and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of polysulfone into epoxy resin improves the toughness to an appreciable extent with insignificant increase in stress–strain properties. DSC studies indicated that the introduction of polysulfone decreases the glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of polysulfone as well as BMI modified epoxy resin show a unimodal reaction exotherm. The thermal stability and flame retardant properties of cured epoxy resins were improved with the introduction of bismaleimide and polysulfone. Water absorption characteristics were studied as per ASTM method and the morphology of the BMI modified epoxy and PSF‐epoxy systems were studied by scanning electron microscope. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis of wood‐based epoxy resins and their mechanical and adhesive properties

Wood‐based epoxy resins were synthesized from resorcinol‐liquefied wood. Wood was first liquefied in the presence of resorcinol with or without a sulfuric acid catalyst at high temperature. Because of the hydroxyl groups, the resorcinol‐liquefied wood was considered as a precursor for synthesizing wood‐based epoxy resin. Namely, the phenolic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition. By the glycidyl etherification, epoxy functionality was introduced to the liquefied wood. The epoxy functionality of the resins was controlled by the concentration of phenolic OH groups in the liquefied wood, which would be a dominant factor for crosslink density and properties of the cured epoxy resins. The flexural strength (150–180 MPa) and the modulus of elasticity (3.2 GPa) of the highly crosslinked wood‐based epoxy resin were equivalent to those of the commercially available epoxy resin, diglycidyl ether of bisphenol A (DGEBA). Also, the shear adhesive strength of the wood‐based epoxy resin was higher than that of DGEBA when plywood was used as the adhesive substrates. The mechanical and adhesive properties suggested that the wood‐based epoxy resins would be well suited for matrix resins of natural plant‐fiber reinforced composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2285–2292, 2006     

Synthesis and film properties of epoxy esters modified with amino resins from glycolysis products of postconsumer PET bottles

Glycolysis of waste polyethylene terephthalate (PET) flakes obtained from grinding postconsumer bottles was carried out at 225–250°C and molar ratios of PET/ethylene glycol were taken as 1/1, 1/1.5, 1/5, and 1/10. Reaction product was extracted by hot water for three times and water‐soluble crystallizable fraction and water‐insoluble fraction were obtained. These fractions were characterized by acid and hydroxyl value determinations, differential scanning calorimeter analysis, and ¹H‐NMR analysis. Glycolysis product was used for synthesis of PET‐based epoxy resin. This epoxy resin was used to prepare epoxy ester resins having 40% and 50% oil content. Epoxy ester resin having 40% oil content was modified with urea‐formaldehyde and melamine‐formaldehyde resins for synthesis of epoxy ester–amino resin. Physical and chemical film properties of epoxy ester and modified epoxy ester resins were investigated. All the epoxy ester and modified epoxy ester films were having excellent adhesion, water, and salt water resistance properties. Modification of PET‐based epoxy ester resins with amino resin has significantly improved hardness, impact resistance, and alkaline and acid resistance of resin films. As a result, PET oligomers obtained from glycolysis of postconsumer PET bottles are suitable for manufacturing of amino‐resin‐modified epoxy ester resins that have improved physical and chemical surface coating properties. POLYM. ENG. SCI., 55:2519–2525, 2015. © 2015 Society of Plastics Engineers     

Synthesis,characterization, and properties of a novel epoxy resin containing both binaphthyl and biphenyl moieties

A new epoxy resin containing both binaphthyl and biphenyl moieties in the skeleton (BLBPE) was synthesized and confirmed by electrospray ionization mass spectroscopy, ¹H‐nuclear magnetic resonance spectroscopy, and infrared spectroscopy. To evaluate the combined influence of two moieties, one epoxy resin containing binaphthyl moiety and another containing biphenyl moiety were also synthesized, and a commercial biphenyl‐type epoxy resin (CER3000L) was introduced. Thermal properties of their cured polymers with phenol p‐xylene resins were characterized by differential scanning calorimetry, dynamic mechanical, and thermogravimetric analyses. The cured polymer obtained from BLBPE showed remarkably higher glass transition temperature and lower moisture absorption, as well as comprehensively excellent thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of rubber/matrix interfacial modifications on the properties of a rubber-toughened epoxy resin

The interface of a rubber-toughened epoxy resin was modified by using epoxide end-capped carboxyl-terminated butadiene and acrylonitrile random copolymer (CTBN). The end-capping epoxides were formulated with different ratios of flexible diglycidyl ether of propylene glycol (DER732) and rigid diglycidyl ether of bisphenol-A (Epon 828). The microstructure and the fracture behavior of these rubber-modified epoxy resins were studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The thermal and mechanical properties were also investigated. With an increase in the amount of end-capping DER732, the interfacial zone of an undeformed rubber particle and the degree of cavitation of the rubber cavity on the fracture surface were greatly increased. At the maximal addition of DER732, fracture energy (GIc) for this toughened epoxy resin containing 10phr CTBN rubber increases up to 2.4 fold compared to that of a conventional CTBN-toughened epoxy resin, but the thermal and the mechanical properties remained quite unaffected. The modification on the interfacial property provides a new technique in the improvement of fracture toughness of a rubber-toughened epoxy resin.