Vulcanization of 1-chlorobutadiene–butadiene rubber with diepoxy compound

Diepoxy vulcanization system of 1-chlorobutadiene–butadiene rubber(CB–BR) having hydroxyl groups with diglycidyl ether of bisphenol A (DGEBA) was studied in the presence of acid anhydrides. Phthalic anhydride (PAn), hexahydrophthalic anhydride (HAn), maleic anhydride (MAn), and succinic anhydride (SAn) were investigated as occuring agents. The results of this investigation indicated that the hydroxyl groups attached to the polybutadiene backbone react with DGEBA to afford a CB–BR vulcanizate rate depended on the kinds of acid anhydrides in the following order: PAn > MAn > SAn > HAn. It is assumed that the reaction between the hydroxyl group in CB–BR and acid anhydride was the rate-determining step. The vulcanization of CB–BR with a higher amount of DGEBA afforded resinous rubber vulcanizates. Thus, DGEBA was concluded to act not only as a curing agent, but also as a reinforcing agent for CB–BR. © 1995 John Wiley & Sons, Inc.     

Enzyme‐catalyzed copolymerization of oxiranes with dicarboxylic acid anhydrides

Ring‐opening copolymerizations of the oxiranes glycidyl phenyl ether (GPE) and diglycidyl ether of bisphenol A (DGEBA) with a dicarboxylic acid anhydride [methyl hexahydrophthalic anhydride, nadic anhydride, maleic anhydride (MA), or itaconic anhydride (IA)] were carried out with the lipases Candida cylindracea (CCL), Lipozyme TL‐IM (LIM), and Novozyme 435 (N435) as catalysts. The CCL‐catalyzed reaction of DGEBA with MA or IA (at a 1:2 molar ratio) at 80°C resulted in only partial curing. We monitored the reactions by Fourier transform infrared spectroscopy and by following the changes in the intensities of carbonyl stretching frequencies of the anhydride and ester groups. The reactivity of the oxirane group in GPE was higher than that in DGEBA; this may have been due to the higher viscosity of DGEBA. The reactivities of the enzymes for the copolymerization of the oxiranes and dicarboxylic acid anhydride were in the order LIM > CCL > N435. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 697–704, 2005     

Studies on the curing and thermal behaviour of DGEBA in the presence of bis(4‐carboxyphenyl) dimethyl silane

The curing behaviour of diglycidyl ether of bisphenol‐A (DGEBA) was investigated by differential scanning calorimetry using bis(4‐carboxyphenyl) dimethyl silane (CPA) as a crosslinking agent and imidazole as a catalyst. Two exotherms were observed in the absence of catalyst in the temperature range 166–328 °C. A significant decrease in the curing temperature was observed when 0.1% imidazole was used as catalyst. Further increase in the concentration of imidazole resulted in a decrease in the peak exotherm temperature. The effect of stoichiometry of functional groups on the curing behaviour of DGEBA was investigated by taking varying mole ratios of CPA, ranging from 1 to 2.5, keeping the concentration of imidazole as 0.1% w/w. The heat of polymerization (ΔH) was found to be maximum at a molar ratio of 1:1.75 (DGEBA:CPA). Mixtures of diaminodiphenyl sulfone (DDS and CPA or phthalic anhydride (PA) and CPA in ratios of 1:0, 0.25:0.75, 0.5:0.5, 0.75:0.25) were also used to investigate the curing behaviour of DGEBA. A significant decrease in curing temperature of DGEBA/DDS was observed on partially replacing DDS with CPA, whereas marginal change in the curing temperatures was observed on replacing phthalic anhydride with CPA. The thermal stability of epoxy resin, cured isothermally, was evaluated by recording thermogravimetry/dynamic thermogravimetry traces in nitrogen atmosphere. The percentage char yield was highest for the sample cured using 1.75 mole of CPA. Copyright © 2003 Society of Chemical Industry     

香草醇基环氧树脂的合成、固化动力学及性能

以可再生香草醇为原料,合成了一种生物基环氧树脂（DGEVA）。通过使用甲基六氢苯酐（MeHHPA）作为固化剂,制备了一种新型的生物基环氧树脂交联网络（DGEVA/MeHHPA）。对其非等温固化动力学、热性能、热机械性能、机械性能和微观形貌结构进行了系统的研究,并用商用的石油基双酚A型环氧树脂组成的石油基环氧树脂体系（DGEBA/MeHHPA）进行对比。结果表明：DGEVA/MeHHPA和DGEBA/MeHHPA具有相似的固化反应活性。DGEVA/MeHHPA具有可以与DGEBA/MeHHPA相媲美的综合性能：玻璃化转变温度为82.2℃;拉伸强度和拉伸模量分别是 (66.7±6)MPa和 (2.8±0.1)GPa;T_d5%、T_d10%和T_dmax分别是242.4℃、284.9℃和392.4℃。此外,DGEVA/MeHHPA在形变过程中发生了塑性变形而吸收了更多的断裂能。DGEVA刚性骨架和低分子量带来的潜在高交联密度赋予了DGEVA优异性能,具有在实际应用中替代石油基环氧树脂的应用潜力。     

Rheological,mechanical, and morphological studies of epoxy/poly(methyl methacrylate) semi‐interpenetrating polymer networks

Semi‐interpenetrating polymer networks (semi‐IPNs) of epoxy resin and poly(methyl methacrylate) (PMMA) were synthesized. Methyl methacrylate (MMA) was polymerized by free radical mechanism with azo‐bis‐isobutyronitrile in the presence of oligomeric epoxy resin (DGEBA), and hexahydrophthalic anhydride as crosslinking agent. The gelation and vitrification transitions during cure/polymerization processes have been examined using parallel‐plates rheological technique. From differential scanning calorimetry and rheological techniques, it was suggested that both curing and polymerization processes occur simultaneously. However, the gelation time was longer for the semi‐IPN than those observed for the cure of pure DGEBA or polymerization of MMA. The gelation time increased significantly when 5% of MMA was employed, suggesting a diluent effect of the monomer. Higher amount of MMA resulted in a decrease of gel time, probably because of the simultaneous polymerization of MMA during the curing process. Structural examination of the semi‐IPNs, using scanning electron microscopy, revealed phase separation in nanoscale size for semi‐IPNs containing PMMA at concentrations up to 15%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Use of eugenol and rosin as feedstocks for biobased epoxy resins and study of curing and performance properties

In this study, an epoxy based on eugenol and an anhydride curing agent based on rosin were prepared. Curing of the eugenol epoxy with a commercial anhydride curing agent and with the rosin‐derived anhydride curing agent was studied. For comparison, a commercial bisphenol A type epoxy, DER353, was also selected in the curing study. The syntheses of the eugenol epoxy and rosin anhydride were investigated and the chemical structures of the products and intermediates were characterized using ¹H NMR and Fourier transform infrared spectroscopies. Non‐isothermal curing of the eugenol epoxy with hexahydrophthalic anhydride and the rosin‐derived maleopimaric acid was studied using differential scanning calorimetry. Thermomechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetric analysis, respectively. Addition of 2‐ethyl‐4‐methylimidazole as catalyst greatly decreased the curing temperature and promoted the completion of cure reactions. The results suggest that the eugenol epoxy and the bisphenol A type epoxy have similar reactivity, dynamic mechanical properties and thermal stability. © 2013 Society of Chemical Industry     

Investigations on the curing of epoxy resins with hexahydrophthalic anhydride

The bifunctional epoxides bisphenol A diglycidyl ether (BADGE) and hexahydrophthalic diglycidyl ester (HHDGE) as well as the monoepoxides phenyl glycidyl ether (PGE) and cyclohexane carboxylic acid glycidyl ester (CHGE) were cured with hexahydrophthalic anhydride (HHPA) in the presence of benzyldimethylamine (BDMA) or 1-methylimidazole (1-MI) as catalysts at 100–140°C. Investigations of the curing kinetics gave sigmoidal-shaped curves with marked induction periods. IR analysis of the cured products revealed that the propagation proceeds not only by the esterification reaction of epoxide with anhydride but also by chain anhydride formation by the reaction of carboxylate with anhydride groups. ¹³C-NMR investigations of the soluble polymers showed that most of the peaks resulting from double bonds could not be assigned to structures formed by initiation reactions that had previously been proposed for the anhydride curing of epoxides. In analogy to a postulated mechanism for the decarboxylation condensation of HHPA alone in the presence of tertiary amines, it is proposed that an isomerization product of HHPA is one of the molecules that initiate the curing reaction.     

Polymerization‐induced bimodal phase separation in a rubber‐modified epoxy system

The bimodal phase separation process of a rubber‐modified epoxy system, consisting of diglycidyl ether of bisphenol A (DGEBA), and a hydroxyl‐terminated butadiene–acrylonitrile random copolymer (HTBN), during curing with tetrahydro‐phthalic anhydride was studied by time‐resolved small‐angle light scattering (TRSALS), differential scanning calorimetry (DSC), and digital image analysis (DIA). The HTBN/DGEBA mixture reveals an upper critical solution temperature (UCST). At higher curing temperatures, double‐peak structure from the matrix was investigated by TRSALS and confirmed by DIA. The special two characteristic size distribution behavior was explained qualitatively by nucleation growth coupled with spinodal decomposition (NGCSD) and the competition between phase separation and polymerization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 59–67, 1999     

An ellipsometric study of polymer film curing: 2,6-Bis(3-aminophenoxy) benzonitrile/4,4′oxidiphthalic anhydride poly(amic acid)

The curing of 2,6-bis(3-aminophenoxy)benzonitrile/4,4′oxidiphthalic anhydride ((β-CN) APB/ODPA) has been investigated using spectroscopic ellipsometry on films with various degrees of imidization. Results indicate that much of the film imidization is accomplished at 200 °C and above. Three absorption peaks have been observed (4.1, 5, and 6 eV) which correspond to intra- and inter-molecular optical transitions. A comparison of the film optical constants for the pristine poly(amic acid) and the fully cured polyimide shows film densification upon imidization. A curing timeline has been obtained using in situ real-time spectroscopic ellipsometry, and ellipsometry is shown to serve as a general technique for studying organic film curing.     

用FTIR研究环氧树脂的固化反应

采用傅里叶变换红外光谱研究了双酚Ａ型环氧树脂／马来酸酐固化剂／咪唑类固化催化剂体系的固化反应。结果表明,固化催化剂的用量在０．２％～２．０％（质量分数）时,对环氧树脂与固化剂的反应可起到明显的催化作用;大于２．０％时反应机理发生显著变化,环氧树脂与催化剂优先反应,抵制环氧树脂与固化剂的反应。     

Intercalation and exfoliation of clay nanoplatelets in epoxy‐based nanocomposites: TEM and XRD observations

Diglycidyl ether of bisphenol A (DGEBA) and diglycidyl ether of bisphenol F (DGEBF) reinforced with organo‐montmorillonite clay nanoplatelets were investigated using anhydride‐ and amine‐curing agents. The sonication technique was used to process epoxy/clay nanocomposites. The basal spacing of clay nanoplatelets was observed by wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS) techniques, and transmission electron microscopy. It was found that the basal spacing of clay nanoplatelets in epoxy matrix was expanded after mixing with either DGEBA/DGEBF or methyltetrahydrophthalic‐anhydride (MTHPA) curing agent. The sonication technique provided larger d‐spacing of clay nanoplatelets. Because of the different curing temperatures, MTHPA‐cured epoxy/clay nanocomposites produced more expanded d‐spacing of clay nanoplatelets modified with methyl, tallow, bis(2‐hydroxyethyl) quaternary ammonium (MT2EtOH) than triethylenetetramine‐cured nanocomposites. Depending on the selection of curing agent and organic modification for clay nanoplatelets, the d‐spacing was expanded to be up to 8.72 nm. POLYM. ENG. SCI., 46:452–463, 2006. © 2006 Society of Plastics Engineers     

水性聚氮酯的合成及其激活反应研究

聚乙二醇（PEG-1000）与甲基六氢苯酐（MHHPA）在催化剂XCT-cat81的存在下生成聚酯多元醇,再在催化剂XCT-cat57存在下,再与二苯基甲基4,4’-二异氰酸酯（MDI）反应生成聚氨酯预聚体,最后用苯酚封端制得水性聚氨酯。使用FTIR红外光谱仪分别对聚酯多元醇和水性聚氨酯进行了表征。使用大分子聚胺XCT-802及低分子二乙烯三胺（DETA）两种固化剂研究了水性聚氨酯封端基的激活反应,讨论了二种固化剂在不同固化温度与固化时间对水性聚氨酯木材黏结强度的影响。     

Comparison of microwave and thermal cure of epoxy–anhydride resins: Mechanical properties and dynamic characteristics

The objective of this work was to compare the mechanical properties of epoxy resins cured by thermal heating and microwave heating. Epoxy–anhydride (100:80) resins were cured in a domestic microwave oven and in a thermal oven. The hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Three types of accelerators were employed. Thermal curing was performed at 150°C for 20 and 14 min for resins containing 1 and 4% accelerator, respectively. Microwave curing was carried out at a low power (207 or 276 W) for 10, 14, and 20 min. All cured resins were investigated with respect to their tensile properties, notched Izod impact resistance, and flexural properties (three‐point bending) according to ASTM standards. The tan δ and activation energy values were investigated with dynamic mechanical thermal analysis, and the extent of conversion was determined with differential scanning calorimetry. The differences in the mechanical properties of the thermally cured and microwave‐cured samples depended on the resin formulation and properties. Equivalent or better mechanical properties were obtained by microwave curing, in comparison with those obtained by thermal curing. Microwave curing also provided a shorter cure time and an equivalent degree of conversion. The glass‐transition temperatures (tan δ) of the thermally and microwave‐cured resins were comparable, and their activation energies were in the range of 327–521 kJ/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1442–1461, 2005     

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     

CTBN/PI复合改性环氧树脂的结构与性能

采用端羧基丁腈橡胶（CTBN）和聚酰亚胺树脂（PI）为改性剂,甲基六氢苯酐（MeHHPA）为固化剂,2,4,6-三（二甲氨基甲基）苯酚（DMP-30）为固化促进剂,对双酚A型环氧树脂（DGEBA)进行改性,研究了CTBN/PI复合改性剂对DGEBA力学性能、动态热力学性能和形态结构的影响。结果表明,CTBN/PI复合改性剂在保持弹性模量损失很小的情况下,显著提高了DGEBA的冲击强度、断裂强度和断裂伸长率;当复合改性体系中CTBN和PI添加量分别为20~30份、1.5~2.0份（质量份,下同）时,体系的综合力学性能最佳;适当引入PI增加了体系储能模量和耐热性,DGEBA的冲击断面发生了塑性变形,韧性得到了改善。     

Curing reaction of diglycidylesters containing alicyclic imide structures with anhydrides and amines as hardeners

The cure reaction of diglycidyl esters containing bicyclo[2.2.2]oct-7-ene units with phthalic annhydride, hexahydrophthalic anhydride, bis(4-aminophenyl)methane, and bis(4-aminophenyl)ethane as hardeners was studied by differential scanning calorimetry. The use of 4-dimethylaminopyridine as a catalyst agent for the anhydride–epoxide reaction was also investigated. Depending on the curing agent, anhydride or amine, and the concentration of the catalyst, differences in activation energies were found, but negligible changes are observed between both anhydrides and the two primary amines. Thermal properties of the final product were unaltered by the hardener used. © 1995 John Wiley & Sons, Inc.     

Rheological and mechanical behaviour of tetraglycidyldiaminodiphenylmethane (TGDDM)/anhydride epoxy systems

The curing of tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) cured with hexahydrophthalic anhydride, tetrahydrophthalic anhydride and nadic methyl anhydride was studied using static rheological techniques under isothermal conditions in different temperature ranges for each system. 1:1 and 1:0.5 stoichiometric ratios were used in all three TGDDM/anhydride systems analysed. From the gelation times of each system at the different conditions employed activation energies were calculated. Flexural mechanical properties, such as elastic modulus, strength and strain to break, were also investigated for all the three TGDDM/anhydride systems employed for different anhydride weight contents which ranged from 0.5 to 1.34 parts of the anhydride weight corresponding to the stoichiometric composition. Possible reasons to explain the mechanical behaviour shown are discussed.     

Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil

Mechanical and thermal properties of materials prepared by curing epoxidized soybean oil with various cyclic acid anhydrides in the presence of tertiary amines were investigated by dynamic mechanical thermal analysis and thermogravimetry. All samples presented thermoset material characteristics that were dependent upon the type of anhydride, the anhydride/epoxy molar ratio, and epoxy group content. The thermosets obtained from anhydrides with rigid structures as such phthalic, maleic, and hexahydrophthalic showed higher glass transition temperatures (Tg) and cross-linking densities. As expected, the Tg decreased as the anhydride/epoxy ratio decreased. The influence of the degree of epoxidation of soybean oil on the mechanical properties and Tg was also investigated. It was found that the higher the epoxy group amount, the higher the Tg and hardness. Cured resins exhibited thermal stability up to 300°C, except for those prepared with dodecenyl succinic anhydride, which began to decompose at lower temperature. They presented excellent chemical resistance when immersed in 1% wt/vol NaOH and 3% wt/vol H₂SO₄ solutions but poor chemical resistance in the presence of organic solvents.     

Comparison between microwave and thermal curing of glass fiber–epoxy composites: Effect of microwave‐heating cycle on mechanical properties

The objective of this study was to compare the mechanical properties between epoxy composites cured by thermal heating and microwave heating. Epoxy‐anhydride resins reinforced with glass fiber were cured in a domestic microwave oven and in a thermal oven. Hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Microwave curing was carried out at various conditions, including 1‐, 2‐, and 3‐step heating cycle, whereby each cycle employed different power level and time. Mechanical properties were tested according to ASTM standards. It is found that the microwave‐cured composites produced mechanical properties as good as the thermally cured composites. The 2‐ and 3‐step heating cycle used in the microwave curing process produced better mechanical properties higher than those obtained from the microwaved 1‐step and thermally curing process. This is attributed to the slow increase in temperature during the beginning of the microwave curing process whereby the very low power level was applied in the first cycle of the multistep heating process. This affected the slower rate of viscosity increment, resulting in better wettability of the glass fiber with enhanced interfacial adhesion between the fibers and the resins. The viscosity of resins affected the homogeneity of the crosslinked structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1059–1070, 2006     

Phosphorus‐containing epoxy resins: Thermal characterization

Three novel aromatic phosphorylated diamines, i.e., bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl} pyromellitamic acid (AP), 4,4′‐oxo bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AB) and 4,4′‐hexafluoroisopropylidene‐bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AF) were synthesized and characterized. These amines were prepared by solution condensation reaction of bis(3‐aminophenyl)methyl phosphine oxide (BAP) with 1,2,4,5‐benzenetetracarboxylic acid anhydride (P)/3,3′,4,4′‐benzophenonetetracarboxylic acid dianhydride (B)/4,4′‐(hexafluoroisopropylidene)diphthalic acid anhydride (F), respectively. The structural characterization of amines was done by elemental analysis, DSC, TGA, ¹H‐NMR, ¹³C‐NMR and FTIR. Amine equivalent weight was determined by the acetylation method. Curing of DGEBA in the presence of phosphorylated amines was studied by DSC and curing exotherm was in the temperature range of 195–267°C, whereas with conventional amine 4,4′‐diamino diphenyl sulphone (D) a broad exotherm in temperature range of 180–310°C was observed. Curing of DGEBA with a mixture of phosphorylated amines and D, resulted in a decrease in characteristic curing temperatures. The effect of phosphorus content on the char residue and thermal stability of epoxy resin cured isothermally in the presence of these amines was evaluated in nitrogen atmosphere. Char residue increased significantly with an increase in the phosphorus content of epoxy network. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2235–2242, 2002