Synthesis of rosin‐based flexible anhydride‐type curing agents and properties of the cured epoxy

BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using ¹H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Effect of the structure of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins

The aim of this study was to determine the effect of the ester carbon chain length of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins. An amine‐terminated prepolymer (i.e., curing agent G) was synthesized from a bisphenol A type liquid epoxy resin and triethylene tetramine. The toughening curing agents (G1 and G2) were prepared by reactions of epoxidized oleic methyl ester and epoxidized oleic capryl ester, respectively, with curing agent G. Fourier transform infrared spectrometry was used to characterize the chemical structure of the curing agents. The effects of the carbon chain length of the oleic ester group in the curing agents on the toughness and other performances of the curing epoxy resins were investigated by analysis of the Izod impact strength, tensile strength, elongation at break, thermal properties, and morphology of the fracture surfaces of the samples. The results denote that the toughness of the cured epoxy resins increased with the introduction of oleic esters into the curing agents without a loss of mechanical properties and that the toughness and thermal stability of the materials increased with increasing ester carbon chain length. The toughness enhancement was attributed to the flexibility of the end carbon chains and ester carbon chains of the oleic esters in the toughening curing agents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and epoxy curing of p‐nonylphenol/dicyclopentadiene adducts

Phenol/dicyclopentadiene adducts were prepared from the BF₃‐catalyzed reaction of p‐nonylphenol and dicyclopentadiene at molar ratios of 2 : 1 and 3 : 2. These dicyclopentadiene‐derived novolac products contain tricyclodecane and multiple phenol functionalities. In curing with diglycidyl ether of bisphenol A, the polymer properties were compared with those cured with formaldehyde novolac or Jeffamine D‐400 amine. When p‐nonylphenol/dicyclopentadiene adducts were mixed with other commercially available curing agents such as Jeffamine D‐400 amine, the tricyclodecane functionality was introduced into the resulting epoxy network. The flexibility of the cured resin was improved due to the presence of the tricyclodecane moiety in the polymer structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2196–2206, 1999     

Epoxy resins from dinaphthols

Epoxy resins were prepared from di-α-naphthol(4,4′-dihydroxy-1,1′-dinaphthyl) and di-β-naphthol(2,2′-dihydroxy-1,1′-dinaphthyl). The resins consisted mainly of the reaction product of 1 mole of dinaphthol with 2 moles of epichlorhydrin. They contained chlorine, however, and were correspondingly deficient in diepoxide functionality. The resins from di-α-naphthol were crystalline, had m.p. 200°C., and were not miscible with conventional curing agents. Di-β-naphthol gave resins with softening points in the range 50–70°C., which cured with diethylenetriamine or the anhydrides of dibasic acids, giving hard but brittle products. The brittleness was not removed by curing with plasticizing curing agents, such as tetrapropenyl succinic anhydride. The cured di-β-naphthol-based resins had thermal stabilities similar to analogous epoxy resins based on bisphenol A.     

生物质环氧树脂固化剂的研究进展

综述了近年来生物质环氧树脂固化剂(BEPCA)的研究进展,主要包括以腰果酚、香兰素、松香、木质素和植物油等作为原料制备的生物质胺类固化剂、生物质酸酐类固化剂和多元酚、羧酸及酯类生物质固化剂等;详细介绍了上述BEPCA的结构、制备方法、合成路线以及其固化产物的性能;最后,总结并展望了BEPCA未来的发展趋势.     

Effect of curing agent on the properties of mineral silica filled epoxy composites

Polymer materials have been used extensively as the organic substrate materials in electronic packaging industry. The mechanical, thermal, and morphology properties of the alternative low cost composites have been investigated in this article. One of the materials is epoxy resin cured by aliphatic amine, and the other is cured by aromatic amine. It was found that the physical, mechanical, and thermal properties of epoxy resins are strongly depended on the curing agents. Morphology changed differently in these two epoxy‐curing systems. Crosslink density obtained from rubbery modulus in dynamic flexural storage modulus showed aromatic amine functionality group that gives higher crosslink density and increased in physical, mechanical, and thermal properties. POLYM. COMPOS., 29:27–36, 2008. © 2007 Society of Plastics Engineers     

Curing behavior of dicyandiamide/epoxy resin system using different accelerators

Various amounts of dicyandiamide (Dicy), two grades of epoxy resins, i.e. Epiran 06 and Epikote 828, and three different accelerators including benzyl dimethyl amine (BDMA), 3-(4-chlorophenyl)-1,1-dimethyl urea (Monuron) and 2-methyl imidazole (Im) were used in curing of Dicy/epoxy resin system. Both of the used epoxy resins were based on diglycidyl ether of bisphenol A (DGEBA). The effects of type and concentration of accelerators on curing behavior were studied by differential scanning calorimetry (DSC) method in dynamic or non-isothermal mode. The optimum concentration of Dicy for curing of epoxy resins was obtained based on the glass transition temperature of the cured epoxy/Dicy formulations. The maximum glass transition temperature of 139 °C was obtained at the stoichiometric ratio of Dicy to epoxy of 0.65. The results showed that BDMA has a broader curing peak in DSC and starts the cure reaction earlier than the others. However, Monuron has a narrow curing reaction peak with good cure latency. The tensile properties of Dicy-cured Epiran 06 and Epikote 828 epoxy resins reinforced with chopped strand mat showed that these two epoxy resins have similar mechanical properties. For composites based on the Epiran 06 and Epikote 828 reinforced with 40 wt % glass chopped strand mat, tensile strength and modulus were 156 and 153.4 MPa and 11.6 and 12.4 GPa, respectively.     

Aminimide as hardener/curing promotor for one part epoxy resin composition

Three kinds of aminimide compounds were examined as latent hardeners/promotors for epoxy resins. Since aminimides are thermolyzed to generate tertiary amine and isocyanate, the compounds are useful as polymerization initiators for the epoxy group as well as promotors for epoxy–acid anhydride reaction. The pot life was over 30 days at 40°C for a formulated one-part epoxy resin system. In comparison with epoxy resins cured with conventional hardeners, several interesting characteristics of the mechanical and electrical properties were observed. In particular, the epoxy resins cured by aminimides exhibited high tensile strength and high impact strength, which make them excellent curing agents for adhesive applications. The reasons for these unique properties are discussed.     

Toughening of a dicyandiamide-cured epoxy resin: Influence of cure conditions on different rubber modifications

Cure kinetics of modified epoxy resins cured with dicyandiamide are studied. The influence of different heating rates in the curing process, such as curing behavior, morphology, and thermo-mechanical properties, is studied. Additionally, three different post-cure cycles at 180°C are employed. Two butadiene-based toughening agents are used, a carboxyl-terminated polybutadiene-co-acrylonitril (CTBN) prepolymer and a functionalized block copolymer of polytetrahydrofuran and hydroxyl-terminated polybutadiene. The amphiphilic block copolymer enables investigations with a bimodal particle size morphology. All results are contrasted with those of the neat resin and butadiene-free block polymer. Faster curing processes result in smaller average particle sizes and better fracture toughness of the modified epoxy resins. Further improvements are achieved with additional post-cure cycles at 180°C. An increased interfacial adhesion between the particles and the epoxy matrix is considered to be the main mechanism. Optimized lengths of the post-cure process can be determined with the butadiene-based toughening agents indicating a competing thermal degradation. Longer post-cures than 40 min lead to lower fracture toughness in the butadiene-based modified materials. In general, similar influences of the curing and post-curing process on the bimodal and unimodal distributed system can be observed differing in more intense dependencies of the bimodal system.     

Preparation and epoxy curing of novel dicyclopentadiene‐derived Mannich amines

Phenol/dicyclopentadiene (DCPD) adducts were prepared from the BF₃‐catalyzed reaction of p‐nonylphenol and dicyclopentadiene at molar ratios of 2 : 1 and 3 : 2. The phenol‐terminating adducts were consequently reacted with diethylenetriamine and formaldehyde using Mannich reaction conditions. These products containing phenol, amine and tricyclodecane functionalities in the same molecule can be used as epoxy curing agents. The diethylenetriamine was add to the phenol via Mannich reaction at approximately 50% theoretical equivalent. The multiple N H groups in amines and the O H groups in phenols provide crosslinking sites for epoxy resins. The cured epoxy resins show improvement in tensile strength and elongation in comparison with those cured by the poly(oxypropylene) diamine (400 molecular weight) or diethylenetriamine. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2129–2139, 1999     

Mechanical properties of E‐glass fiber reinforced siliconized epoxy polymer composites

Siliconized epoxy‐matrix systems have been developed by an interpenetrating mechanism using epoxy resins GY 250 and LY 556 (Ciba‐Geigy) and hydroxyl terminated polydimethylsiloxane with γ‐aminopropyltriethoxysilane as crosslinker in the presence of dibutyltindilaurate catalyst. Aliphatic amine (HY 951, Ciba‐Geigy), aromatic amine (HT 972, Ciba‐Geigy) and polyamidoamine (HY 840, Ciba‐Geigy) are used as curing agents for epoxy resins. The tentative level of 10% siloxane introduction into epoxy resin has been ascertained from experimental studies to obtain reasonable improvements in the impact behavior without compromising other mechanical properties. The impact behavior of E‐glass reinforced composites made from the siliconized epoxy resin is enhanced to 2–4 times over that measured on the composites made from a pure epoxy resin. Composites cured with aromatic amine impart better mechanical properties than those cured with aliphatic amine and polyamidoamine.     

几种胺类固化剂对环氧树脂固化行为及固化物性能的影响

固化剂结构对环氧树脂的固化行为和固化物性能具有重要影响,本文研究了聚醚胺(D-230)、异佛尔酮二胺(IPDA)和3,3'-二甲基-4,4'-二氨基-二环己基甲烷(DMDC) 3种胺类固化剂与实验室自制的低翻度环氧树脂A进行固化反应.通过薪度分析、红外(FTIR)光谱分析、DSC分析等手段研究了环氧树脂与固化剂反应程度...     

Are cured epoxy resins inhomogeneous?

The alternating mechanism of network formation in the curing of epoxy resins from bisphenol A diglycidyl ether (BADGE) and amine curing agents does not offer any special opportunity for the formation of inhomogeneities caused by partial segregation or inhomogeneous crosslinking. Etched fracture surfaces of resins cured with 4,4′-diaminodiphenylmethane, hexamethylenediamine and hexahydrophthalic anhydride at various initial ratios of BADGE, studied by electron microscopy, reveal globular structures 20–40 nm in size. However, similar structures are observed with etched surfaces of amorphous polystyrene and poly(methyl methacrylate). The small-angle X-ray scattering curves for cured epoxy resins do not differ in principle from those of common amorphous polymers; swelling in a solvent of a lower electron density does not lead to an increase in scattering within the particle size range 10–10² nm. It is pointed out that the physical structure of simple cured epoxy resins does not essentially differ from that of common amorphous polymers. With more complicated systems, a more pronounced inhomogeneity might be caused by thermodynamic incompatibility or by non-alternating mechanisms of the curing reaction.     

Glass Fiber Reinforced Composites and Thermal Study of Flame Retardant Epoxy Resin Systems Using Anhydride Curing Agents

Differential scanning calorimetric (DSC) curing kinetics of the epoxy systems composed of conventional, tetrafunctional, and phosphorylated epoxy resins were investigated using different anhydrides as curing agents and triethylamine as curing catalyst. The dynamic scans were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The thermal stability of the cured epoxy resins was studied by thermogravimetric analysis in nitrogen atmosphere at a heating rate of 10°C/min. Glass fiber reinforced composites were fabricated and evaluated for their limiting oxygen index, mechanical properties, dielectric properties, and chemical resistance. The incorporation of an epoxy fortifier showed significant improvement in mechanical properties.     

固化体系对环氧树脂耐高温性能的影响

针对覆铜板的耐高温要求,分别使用胺类固化剂4,4′-二氨基二苯砜(DDS)、4,4′-二氨基二苯醚(DDE)和乙二胺(EDA)固化改性双酚A型环氧树脂,研制适用于耐高温覆铜板的环氧树脂固化物。用示差扫描量热法(DSC)研究其固化过程,讨论了固化剂用量、固化剂种类及固化温度等因素对固化物玻璃化转变温度(Tg)的影响。实验结果表明,固化物耐热性最好的配比不是化学计量,而是偏离化学计量,在理论用量的基础上适当增加固化剂用量,可有效地提高固化产物的玻璃化温度Tg值;使用芳香胺类固化剂固化双酚A型环氧树脂,其固化产物有较高的玻璃化温度,可以满足覆铜板耐高温的要求。     

Adhesive Properties of Epoxy Resin with Chromic Hardener

Cohesive and adhesive properties have been compared of epoxy resins crosslinked either with chromic‐based hardener or with conventional amine‐type hardener. Higher cohesive parameters, such as yield strength, Young's modulus and impact resistance were observed for the material cured with chromic hardener. The adhesive strength of metal‐metal joints (steel‐aluminium) has been also found to be higher for chromic hardener containing epoxy compared to conventional curing systems. The time dependencies of adhesive strength after thermal treatment at 140°C of the joints showed a higher thermal resistance of the epoxy with chromic hardener when compared to the amine cured resin.     

Dynamic mechanical analysis of rubber toughened epoxy resins

Dynamic mechanical analysis (DMA) was used to characterize cured epoxy resin formulations from ?150°C to temperatures above their α transitions. The resins were aromatic amine and aliphatic amine cured and were modified with carboxylterminated acrylonitrile-butadiene (CTBN) rubbers to improve their toughness, A DuPont 981 dynamic mechanical analyzer was used to measure the modulus and mechanical loss factor (tan δ) of the samples. Changes in the α and β transitions in the scan of tan δ as a function of temperature were related to changes in the formulation. Relations were also sought between changes in the DMA data and fracture and impact toughness of the cured formulations obtained using an instrumented impact test. Impact tests were performed at ?196°C and at room temperature. Results indicate that fracture toughness and the dynamic mechanical properties are affected by the amount of rubber, the compatibility of the rubber and epoxy, and changes in the curing agent stoichiometry.     

Effect of Phenol/Formaldehyde Stoichiometry on the Modification of Epoxy Resin Using Epoxidized Novolacs

ABSTRACT

Unmodified epoxy resins based on bisphenol A exhibit brittleness and low elongation after cure. This article reports the results of a study for improving the properties of epoxy resin by blending with suitable thermosets. Hybrid polymer networks of diglycidyl ether of bisphenol A (DGEBA) resin with epoxidized phenolic novolac resins (EPN) containing phenol and formaldehyde in different stoichiometric ratios were prepared by physical blending. The modified epoxy resins were found to exhibit improved mechanical and thermal properties compared to the neat resin. DGEBA resins containing 2.5 to 20 wt% of epoxidized novolac resins (EPN) prepared in various stoichiometric ratios (1:0.6, 1:0.7, 1:08, and 1:0.9) between phenol and formaldehyde were cured using a room temperature amine hardener. The cured samples were tested for mechanical properties such as tensile strength, modulus, elongation, and energy absorption at break. All the EPNs are seen to improve tensile strength, elongation, and energy absorption at break of the resin. The blend of DGEBA with 10 wt% of EPN-3 (1:0.8) exhibits maximum improvement in strength, elongation, and energy absorption. EPN loading above 10 wt% is found to lower these properties in a manner similar to the behavior of any filler material. The property profiles of epoxy–EPN blends imply a toughening action by epoxidized novolac resins and the extent of modification is found to depend on the molar ratio between phenol and formaldehyde in the novolac.     

Maleimide-epoxy resins: preparation, thermal properties, and flame retardance

Maleimide modified epoxy compounds were prepared through reacting N-(4-hydroxylphenyl)maleimide (HPM) with diglycidylether of bisphenol-A. Triphenylphosphine and methylethylketone were utilized in the reactions as a catalyst and a solvent, respectively. The resulting compounds possessed both oxirane ring and maleimide group. The kinetics of the curing reactions of the maleimide-epoxy compounds and amine curing agents, 4,4-diaminodipheylmethane (DDM) and dicyandiamide (DICY), were studied. Incorporation of maleimide groups into epoxy resins provided cyclic imide structure and high cross-linking density to the cured resins, to bring high glass transition temperatures (179 °C) and good thermal stability (above 380 °C) to the cured resins. High char yields in the thermogravimetric analysis and high limited oxygen index values (25.5-29.5) were also observed for the cured resins to impy their good flame retardance.