Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.     

Modification of aromatic diamine-cured epoxy resins by poly(oxymethylene) or hybrid modifiers containing poly(oxymethylene)

A copolymer comprising poly(oxymethylene) (POM, polyacetal) was used to improve the fracture toughness of a resin based on diglycidyl ether of bisphenol A (DGEBA) cured with 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenyl methane. POM was a less effective modifier for epoxies and a third component was used as a toughener or a compatibilizer for POM. The third component includes polypropylene glycol-type urethane prepolymer (PU) and aromatic polyesters. The hybrid modifiers composed of POM and PU were more effective as modifiers for toughening epoxies than POM alone. In the ternary DGEBA/POM/PU (90/10/10wt ratio) blend, the fracture toughness, K_IC, for the modified resin increased 50% with retention of flexural properties and a slight decrease in glass transition temperature (T_g) compared with those of the unmodified epoxy resin. The aromatic polyesters include poly(ethylene phthalate) (PEP), the related copolyesters and poly(butylene phthalate). PEP was most effective of them as a third component in the hybrid modifier. In the ternary DGEBA/POM/PEP (85/15/10) blend, K_IC for the modified resin increased 70% with medium loss of flexural strength and retention of T_g. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviour of the modified epoxy resin systems. ©1997 SCI     

双马来酰亚胺及聚醚酮树脂改性环氧树脂的研究进展

综述了双马来酰亚胺及聚醚酮类树脂改性环氧树脂的研究及应用情况。     

Toughening of epoxy resins by modification with aromatic polyesters

Aromatic polyesters, prepared by the reaction of phthalic or isophthalic acids and α,ω-alkanediols, were used to reduce the brittleness of bisphenol-A diglycidyl ether epoxy resin cured with methyl hexahydrophthalic anhydride. These polyesters were effective as modifiers for toughening of the epoxy resin system. The most suitable composition for modification of the epoxy resins was inclusion of 20 wt % of poly(ethylene phthalate) (MW 7200), which resulted in a 150% increase in the fracture toughness (K_IC) of the cured resin at no expense of its mechanical properties. The effectiveness of poly(alkylene phthalate)s as modifiers decreased with increasing the chain length of alkylene units. The toughening mechanism was discussed based on the morphological and dynamic mechanical behaviors of the modified epoxy resin system.     

Viscoelastic behaviour of epoxy resins modified with poly(methyl methacrylate)

The viscoelastic behaviour of a stoichiometric diglycidyl ether of bisphenol-A, (DGEBA), 4,4′-diaminodiphenylmethanes (DDM)s epoxy matrix modified with several amounts of poly(methyl methacrylate) (PMMA) has been studied by dynamic-mechanical analysis. Mixtures pre-cured at 80°C ranged from transparency to opacity as thermoplastic content changed from 5 to 15wt%. These changes have been attributed to variations in the ratio between polymerization rate and phase separation rate when PMMA content increased in the mixtures. When PMMA segregated from the epoxy matrix during curing, it had no influence on the crosslinking density of the epoxy phase. The clear decrease of temperature and activation energy of the β relaxation with respect to those values for the neat matrix, observed for the 5wt% PMMA-containing mixture but not for the 15wt% PMMA-containing one, are proposed to be a consequence of physical interactions between the PMMA chains and some epoxy oligomers. The dissimilar variation of the height of the ω relaxation with frequency when compared to that for the other relaxations studied, outlines the significance of physical factors influencing this relaxation. © 1998 Society of Chemical Industry     

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.     

环氧树脂的水性化

对环氧树脂水性化的主要进展进行了综述,侧重对水性环氧乳化技术、成膜机理及一些相关问题进行了简单分析.     

Preparation and characterization of poly(urea-formaldehyde) microcapsules filled with epoxy resins

The preparation of microcapsules applied to the fabrication of self-healing composites has been paid more attentions. A new series of microcapsules were prepared by in situ polymerization technology with poly(urea-formaldehyde) (PUF) as a shell material and a mixture of epoxy resins (diglycidyl ether of bisphenol A: DGEBPA) and 1-butyl glycidyl ether (BGE) as core materials. The microencapsulating process of core material was monitored using optical microscopy (OM). The chemical structure of microcapsule was characterized using Fourier-transform infrared spectroscopy (FTIR). Morphology and shell wall thickness of microcapsule were observed using metalloscope (MS), scanning electron microscopy (SEM) and OM, respectively. The effects of different pre-polymers, weight ratios of urea to formaldehyde (U-F) and the agitation rates on the physical properties of microcapsules were investigated. The storage stability of microcapsules at different times and temperatures was analyzed. The thermal properties of microcapsules were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results indicate that PUF microcapsules containing epoxy resins can be synthesized successfully, and during the microencapsulation, the epoxide rings in epoxy resins are hardly affected by the surrounding media. The rough outer surface of microcapsule is composed of agglomerated PUF nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 238 °C.     

溴化环氧对聚氨酯涂料的阻燃改性研究

通过使用溴化环氧树脂对聚氨酯涂料进行的阻燃改性,制得了具有阻燃功能的聚氨酯涂料。研究了溴化环氧及协同剂Sb2O3用量对聚氨酯涂料阻燃性能和涂膜硬度、光泽度的影响。结果表明当溴化环氧用量为10%,在3%的Sb2O3协同作用下,可将聚氨酯涂料的极限氧指数(LOI)从18提高到30,同时能保证聚氨酯涂料优良的物理机械性能。     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Curing reaction of epoxy resins with diamines

The curing reaction of a commercial bisphenol A diglycidyl ether (BADGE) with ethylenediamine (EDA) was studied by differential scanning calorimetry. Different kinetic expressions were found with isothermal (low temperature range) and dynamic (high temperature range) runs. Two competitive mechanisms are shown to be present: an autocatalytic one (activation energy E = 14 kcal/mol) and a noncatalytic path characterized by a second-order reaction with E = 24.5 kcal/mol. At low temperatures both mechanisms took place simultaneously, showing a significant decrease in the reaction rate after the gel point. At high temperatures only the noncatalytic reaction was present, without showing a noticeable rate decrease in the rubber region. Also, a third-order dependence of the glass transition temperature on reaction extent is shown.     

Chemical modification of epoxy resins by dialkyl(or aryl) phosphates: Evaluation of fire behavior and thermal stability

The improvement of flame-retardation of thermosetted epoxy–amine resins was attempted by chemically incorporating phosphorus-containing reagents. By reacting 4,4′-diglycidylether of bisphenol A (DGEBA) with dialkyl (or aryl) phosphate, it was possible to chemically modify the epoxy resin and then cure it in the presence of 4,4′-diaminodiphenylsulfone (DDS) to obtain epoxy-amine resin with good flame-retardant and thermal stability behaviors. The quantitative aspect of the addition of dialkyl (or aryl) phosphate onto glycidyle oxiranes was evaluated by elemental analysis of the modified epoxy-amine resins. Flammability and thermal behaviors of modified DGEBA/DDS resins depend on the nature of phosphate groups (the best flame-retardation was observed on resins bearing phenyl phosphate groups) and their concentration in the material. In relation to DGEBA/DDS samples containing additives of the same structure [trialkyl(or aryl) phosphate], cured resins incorporating chemically bonded phosphate groups show a better flame-retardation. On the contrary to the nonomodified DGEBA/DDS [with or without trialkyl (or aryl) phosphate as additive], combustion of modified DGEBA/DDS resins is accompanied by formation of intumescent char. Chemical modification of DGEBA by dialkyl (or aryl) phosphates can be carried out in situ during the curing of epoxy resins without change in the fire behavior. © 1996 John Wiley & Sons, Inc.     

Structural heterogeneity of suspension poly(vinyl chloride) resins

Morphology of poly(vinyl chloride) resin particles formed by suspension polymerization was investigated by a combination of several techniques. Significant differences were found in the internal structure of resins obtained under different polymerization conditions. Five main types of resin particles with different porosity and absorptivity were identified by scanning electron microscopy. Three methods were employed to characterize porosity and structural heterogeneity of resin particles: density fractionation of resin particles in mixtures of methanol and carbon tetrachloride; absorption of silicone oil and dioctyl phthalate by resin particles; and examination of fractured particles embedded in epoxy resins. All three methods gave consistent results and can be used for semiquantitative characterization of resin structural heterogeneity. Different particle structure and degree of resin heterogeneity: can profoundly affect compounding and processing operations.     

Toughening of epoxy systems by brominated epoxy

Blends of brominated epoxy (BE) and conventional epoxy resins were studied following curing with aliphatic triethylenetetramine (TETA), etheric (polyether diamine‐ PEA4), and aromatic (3,3′‐diamino diphenyl sulfone [DDS]) hardeners. The addition of BE resulted in an increase in T_g in all tested blends. Blends with 50 wt% BE cured with TETA demonstrated an increase in flexural modulus and flexural strength, while preserving the elongation. Blends with 40 wt% BE cured with PEA4 and 50 wt% BE cured with DDS resulted in a significant enhanced tensile elongation. The shear strength of all cured systems decreased moderately with the addition of BE exhibiting a mixed mode failure. Analysis of the fracture morphology using electron microscopy supported the increase of toughness levels as a result of incorporating BE to conventional epoxy. A unique nodular and rough fracture morphology was obtained, which is related to a toughening mechanism caused by the addition of BE. It was concluded that blends of BE and conventional epoxy could be used as structural adhesives having high T_g, enhanced mechanical properties and increased toughness. POLYM. ENG. SCI., 59:206–215, 2019. © 2018 Society of Plastics Engineers     

原位聚合法制备脲醛树脂包覆环氧树脂微胶囊

以脲醛树脂为囊壁、环氧树脂E-51的乙酸乙酯溶液为囊芯,采用原位聚合法成功制备了脲醛树脂包覆环氧树脂溶液的微胶囊。通过改变尿素、甲醛、芯材用量等研究了脲醛树脂生成速率和沉积速率对微胶囊形貌和结构的影响。利用扫描电子显微镜、光学显微镜、傅里叶变换红外光谱仪和热重分析仪对微胶囊进行表征。结果表明:成功制备了外表面粗糙和光滑的两种微胶囊,且这两种微胶囊的芯材都具有良好的流动性;外表面粗糙的微胶囊力学性能较好,热稳定性优良。     

Surface modification of cellulose nanocrystals by grafting with poly(lactic acid)

The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L‐lactide by ring‐opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long‐term stability of a suspension of poly(lactic acid)‐grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X‐ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy. © 2013 Society of Chemical Industry     

Chemical modification of poly(1-butene) resins through reactive processing

Controlled-rheology poly(1-butene) resins have been produced by chemical modification of commodity poly(1-butene) (PB-1) resins through reactive processing with an organic peroxide. Using various amounts of peroxide, samples have been produced and have been analyzed in terms of their molecular and rheological properties. Molecular weight distributions (MWD) as determined by gel permeation chromatography (GPC) indicate that polydispersity (PDI) remains approximately constant but weight-average molecular weight (M_w) decreases with increasing peroxide concentration. These trends are in agreement with predictions from a kinetic model previously developed for the production of controlled-rheology polypropylene. Linear viscoelastic measurements indicate that the modified samples are thermorheologically simple and that zero-shear viscosity decreases with increasing peroxide concentration while flow activation energy remains approximately constant. Finally, no significant variation in melting and crystallization properties was observed for the range of peroxide concentrations used. Based on these results, it is proposed that tailor-made controlled-rheology poly(1-butene) resins can be produced easily through reactive extrusion operations similar to those used for the production of controlled-rheology polypropylene (CRPP).     

脂环族环氧树脂／双酚A环氧树脂共混改性研究

采用脂环族环氧树脂（EPL-4221）与双酚A型环氧树脂E-51共混,用酸酐固化剂和促进剂使其固化,研究脂环族环氧树脂的用量对共混树脂性能的影响及其规律性,包括冲击强度、弯曲强度、拉伸强度、维卡软化点温度、漆膜的粘附力、铅笔硬度、耐磨性以及拉伸剪切强度。结果表明,随脂环族环氧树脂用量的增加,共混树脂的综合性能先增加后降低,脂环族环氧树脂的质量分数为15％-20％时,具有最大值。     

Mechanical and morphological properties of epoxy resins modified by poly(phthalazinone ether sulfone ketone)

A series of blends have been prepared by adding a novel thermoplastic poly(phthalazinone ether sulfone ketone) (PPESK) in varying proportions to diglycidyl ether of bisphenol A epoxy resin (DGEBA) cured with p‐diaminodiphenylsulfone (DDS). All the blends showed two‐phase structures characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Addition of the PPESK resulted in great enhancement of glass transition temperatures (T_g) both in the epoxy‐rich phase and in the PPESK‐rich phase by reason of the special structure of PPESK. There was moderate increase in the fracture toughness as estimated by impact strength. Fracture mechanisms such as crack deflection and branches, ductile microcracks, ductile tearing of the thermoplastic, and local plastic deformation of the matrix were responsible for the increase in the fracture toughness of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445