Toughening of an epoxy anhydride resin system using an epoxidized hyperbranched polymer

This paper reports on the use of an epoxidized hyperbranched polymer (HBP) as an additive to an epoxy anhydride resin system. The hyperbranched polymer used was an aliphatic polyester with a molecular weight of around 10 500 g mol^?1. The epoxy resin mixture used was a combination of a difunctional diglycidyl ether of bisphenol A (DGEBA) epoxy and an epoxy novolac, and was cured with a catalysed anhydride curing agent. It has been shown that, at a concentration range of 0 to 20 wt% addition, the HBP is able to almost double the fracture toughness, with little evidence of any deleterious effects upon processing and the durability of the cured resin system. The flexural modulus and stress, however, were found to both decrease by about 30% as a result of HBP addition while the T_g was found to decrease by about 10%. The processability of the uncured resin systems has been investigated by using rheological and calorimetric techniques and it was found that the processability window, as determined by the gel time and viscosity changes, was relatively unaffected by HBP addition. The fracture surfaces were evaluated by using scanning electron microscopy which showed that the unique structure of the HBP facilitates an enhanced interaction with the polymer matrix to achieve excellent toughness enhancement of the polymer matrix. The durability of the epoxy network has been investigated via thermogravimetric analysis (TGA) and solvent uptake, and the HBP has been shown to have little systematic deleterious effect upon the degradation temperatures and the total amount of solvent absorbed. Copyright © 2003 Society of Chemical Industry     

Toughening of epoxy resin using acrylate‐based liquid rubbers

Carboxyl‐terminated poly(2‐ethylhexyl acrylate) (CTPEHA) liquid rubbers of different molecular weights and functionalities (LR‐1 to LR‐6) were synthesized by bulk and solution polymerization techniques. The liquid rubbers were characterized by nonaqueous titration, vapor pressure osmometry, and gel permeation chromatography. The CTPEHA oligomers were prereacted with the epoxy resin, and the modified epoxy networks were made by curing with an ambient‐temperature curing agent. The impact properties of the modified epoxy networks were evaluated, and the effects of molecular weight, functionality of the liquid rubber, and ductility of the matrix on the impact strength of the modified networks were investigated. The morphology of the toughening behavior was analyzed using a scanning electron microscope. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 716–723, 2000     

新型脂肪族超支化环氧树脂的制备及其改性作用

采用一步法合成了新型脂肪族超支化环氧树脂HTPE-3,利用FT-IR对其结构进行了表征。研究了双酚A型环氧树脂E-51/HTPE-3杂化树脂的力学性能和热性能。结果显示,杂化树脂的韧性和强度随HTPE-3含量的增加先增加后降低,具有极大值;当HTPE-3质量分数为12%左右时,与纯E-51树脂相比,杂化树脂的冲击强度和断裂韧性分别提高了169.8%和35.2%,拉伸强度和弯曲强度分别提高了6.5%,10.0%,维卡软化点温度、玻璃化转变温度和热分解温度略有下降。     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

超支化聚合物在环氧树脂中的应用

综述了超支化聚合物在环氧树脂中的应用,简述了超支化环氧树脂、超支化环氧树脂固化剂和超支化环氧树脂添加剂的合成及应用进展,展望了其研究前景。     

Toughening of epoxy resin using synthesized polyurethane prepolymer based on hydroxyl-terminated polyesters

Epoxy resins are increasingly finding applications in the field of structural engineering. A wide variety of epoxy resins are available, and some of them are characterized by a relatively low toughness. One approach to improve epoxy resin toughness includes the addition of either a rigid phase or a rubbery phase. A more recent approach to toughen brittle polymers is through interpenetrating network (IPN) grafting. It has been found that the mechanical properties of polymer materials with an IPN structure are fairly superior to those of ordinary polymers. Therefore, the present work deals with epoxy resin toughening using a polyurethane (PU) prepolymer as modifier via IPN grafting. For this purpose, a PU prepolymer based on hydroxyl-terminated polyester has been synthesized and used as a modifier at different concentrations. First, the PU-based hydroxyl-terminated polyester has been characterized. Next, an IPN (Epoxy–PU) has been prepared and characterized using Fourier transform infrared (FTIR) spectroscopy, thin-layer chromatography (TLC), and scanning electron microscopy (SEM) prior to mechanical testing in terms of impact strength and toughness. In this study, a Desmophen 1200-based PU prepolymer was used as a modifier at different concentrations within the epoxy resin. The results also showed that, further to the IPN formation, the epoxy and the PU prepolymer reacted chemically (via grafting). Compared to virgin resin, the effect on the mechanical properties was minor. The impact strength varies from 3–9 J/m and K_c from 0.9–1.2 MPa m^1/2. Furthermore, the incorporation of a chain extender with the PU prepolymer as a modifier into the mixture caused a drastic improvement in toughness. The impact strength increases continuously and reaches a maximum value (seven-fold that of virgin resin) at a modifier critical concentration (40 phr). K_c reaches 2.5 MPa m^1/2 compared to 0.9 MPa m^1/2 of the virgin resin. Finally, the SEM analysis results suggested that internal cavitation of the modifier particles followed by localized plastics shear yielding is probably the prevailing toughening mechanism for the epoxy resin considered in the present study. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2603–2618, 1998     

端羧基超支化聚酯改性环氧树脂固化体系研究

利用丁二酸酐对端羟基超支化聚酯(AHBP)的端基进行改性,得到新的端羧基超支化聚酯(CHBP),并将其用于环氧树脂体系的增韧。研究了CHBP用量、羧基含量对环氧树脂/甲基四氢苯酐(EP/MeTHPA)固化体系的力学性能和热性能的影响。结果表明,改性后分子末端全部带羧基的CHBP的增韧作用最好,冲击强度可达18.5kJ/m2。CHBP质量分数为15%时,固化物的冲击强度可达18.2 kJ/m2,拉伸强度64.86 MPa,玻璃化温度(Tg)从100℃提高到106℃左右,可满足增韧环氧树脂的同时不降低其耐热性的要求。     

Mechanical properties of epoxy resin/hydroxyl‐terminated polyester blends: effect of two‐phase structure

In this paper, the effect of two‐phase structure on the mechanism of rubber‐toughening of epoxy resins was studied. Three types of hydroxyl‐terminated polyesters with different molecular weights were synthesized in order to modify epoxy resins to obtain single‐phase (P‐1), critical phase separation (P‐2) and two‐phase (P‐3) structures. The results of dynamical mechanical analysis and scanning electron microscopy distinguished the dissolved and phase‐separated polyesters in the epoxy matrix. The P‐1 system showed the highest dissolved content of polyester in the epoxy matrix, while the P‐3 system exhibited the lowest content. Both dissolved and phase‐separated polyesters proved to be capable of increasing the toughness of modified epoxy resins. The phase‐separated polyester was found to contribute much more to the improvement of toughness. Copyright © 2005 Society of Chemical Industry     

Toughening of epoxy resin blended with thermotropic hydroxyethyl cellulose acetate

Thermotropic hydroxyethyl cellulose acetate (HECA) was totally miscible with uncured epoxy resin, and the miscibility was not influenced by the degree of substitution (DS) of HECA. When the epoxy resin was cured with diamine (DDA), HECA became immiscible with the epoxy resin matrix, and a heterogeneous system was formed. Epoxy resin existed as a constant phase, and HECA-rich domains were dispersed in the matrix with dimensions of about 0.2–0.5 μm. Epoxy resin could be toughened by HECA, and the impact strength of the epoxy resin blends with 10 wt % HECA was the maximum. HECA exhibited the highest toughening ability when the epoxy resin was cured at the temperature at which the HECA existed as a liquid crystalline state. The toughening ability was also influenced by the degree of substitution for acetyl of HECA, and the impact strength of the epoxy resin blends decreased with increasing the DS for acetyl of HECA. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1159–1163, 1998     

Blends of epoxy resin with amine‐terminated polyoxypropylene elastomer: Morphology and properties

A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between G_IC and plateau modulus (above the resin T_g), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999     

丁腈橡胶增韧环氧树脂研究进展

综述了近年来丁腈类橡胶增韧环氧树脂的研究进展,其中包括固体丁腈橡胶,液体丁腈橡胶(丁腈-40液体橡胶,无规端羧基液体丁腈橡胶(CRBN),端羧基液体丁腈橡胶(CTBN),改性端羟基丁腈橡胶(HTBN),改性端氨基液体丁腈橡胶(ATBN))以及改性液体丁腈橡胶与纳米SiO2共同增韧环氧树脂。     

Toughening epoxy resin with blocked isocyanate containing soft chain

A series of imidazole (MI) blocked 2,4‐toluene diisocyanate (TDI) with polyethylene glycol (PEG‐400) as soft segment (PEG‐MI‐b‐TDI) were synthesized for toughening and curing the bisphenol A type epoxy resin (E‐44). Fourier transform infrared (FTIR) spectrum indicates that the NCO groups of the isocyanate molecule are blocked with MI. For curing epoxy systems, elimination of epoxy group and the formation of urethane bonds were studied by FTIR spectroscopy. The results of mechanical property were shown that the tensile shear and impact strengths of neat MI and MI‐b‐TDI cured E‐44 are lower than those of PEG‐MI‐b‐TDI cured E‐44. Based on the scanning electron microscope studies, microstructure evolutions of the E‐44 cured by different curing agents were imaged. The mechanical, thermal, and dynamic mechanical properties were measured by universal testing machine, differential scanning calorimeter and dynamic mechanical analyzer (DMA). The toughness of E‐44 cured by PEG‐MI‐b‐TDI was effectively improved without sacrificing the tensile shear strength. Based on the DMA studies, the long soft chain of PEG brought in a noticeable lowering in the glass transition temperature (T_g). The glass transition temperature is near 165°C for the neat MI cured E‐44, which is higher than the T_gs of the other curing agents cured epoxy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41345.     

Toughening of cycloaliphatic epoxy resin improved by reactive copolymers with flexible alkyl side chains

Reactive copolymers with flexible alkyl side chains were used as modifiers to improve the toughness of a cycloaliphatic epoxy resin. In this study, we used three types of copolymers with different alkyl chain length (C₄H₉, C₆H₁₃, and C₁₀H₂₁). As a result, the system with an added copolymer having the longest alkyl chain length (C₁₀H₂₁) formed a phase separation structure. The addition of this copolymer (C₁₀H₂₁) led to a 50% increase in the fracture toughness (K_IC) of the cured resin at the slight expense of its glass transition temperature. Scanning electron microscope observations in the vicinity of a crack tip after a compact tension test showed that cavitation of the dispersed phase occurred. The crack growth was inhibited and thus the toughness was improved due to the plastic deformation of the epoxy matrix followed by cavitation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Toughness and strength improvement of diglycidyl ether of bisphenol‐A by low viscosity liquid hyperbranched epoxy resin

This article reports on the use of low viscosity liquid thermosetting hyperbranched poly(trimellitic anhydride‐diethylene glycol) ester epoxy resin (HTDE) as an additive to an epoxy amine resin system. Four kinds of variety molecular weight and epoxy equivalent weight HTDE as modifiers in the diglycidyl ether of bisphenol‐A (DGEBA) amine systems are discussed in detail. It has been shown that the content and molecular weight of HTDE have important effect on the performance of the cured system, and the performance of the HTDE/DGEBA blends has been maximum with the increase of content and molecular weight or generation of HTDE. The impact strength and fracture toughness of the cured systems with 9 wt % second generation of HTDE are 58.2 kJ/m² and 3.20 MPa m^1/2, which are almost three and two times, respectively, of DGEBA performance. Furthermore, the tensile and flexural strength can be enhanced about 20%. The glass transition temperature and Vicat temperature, however, are found to decrease to some extent. The fracture surfaces are evaluated by using scanning electron microscopy, which showed that the homogeneous phase structure of the HTDE blends facilitates an enhanced interaction with the polymer matrix to achieve excellent toughness and strength enhancement of the cured systems, and the “protonema” phenomenon in SEM has been explained by in situ reinforcing and toughening mechanism and molecular simulation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2504–2511, 2006     

橡胶增韧环氧树脂的研究

以羧基丁腈橡胶、聚硫橡胶和羟基聚硅氧烷为增韧剂,以冲击强度、弯曲强度和拉伸剪切强度来评价环氧树脂的增韧效果。实验结果表明,加入增韧剂后的各配方韧性相对于对照组均有不同程度的提高;液态聚硫橡胶增韧的环氧树脂胶表现出良好的抗冲击性能和抗弯曲性能;羧基丁腈橡胶增韧的环氧树脂胶表现出良好的拉伸剪切性能。     

核壳聚合物增韧环氧树脂的研究及进展

核壳聚合物(CSP)用来增韧环氧树脂的最大优点,即在提高韧性的同时而不降低材料的Tg和加工性能。综述了核壳聚合物增韧环氧树脂的特点,核壳聚合物的制备方法、微观结构及形态,以及增韧环氧树脂及其复合材料的性能及影响因素。树枝形聚合物作为一种结构特殊的聚合物,也越来越得到广泛的研究和应用。并对环氧树脂的增韧机理进行了阐述,即空穴化-塑性形变。文中还对核壳聚合物及树枝形聚合物增韧环氧树脂进行了展望。     

Toughening of vinyl ester resin using butadiene-acrylonitrile rubber modifiers

A common method for toughening thermoset resins is the addition of butadiene-acrylonitrile based rubber modifiers. A difficulty experienced by diglycidyl ether of bisphenol-A (DGEBA) vinyl esters (VE) compared to other thermosets is the solubility of the butadiene-acrylonitrile modifier. In this study, a miscible system was prepared by reducing the VE monomer molecular weight to 540 g/mol from industrially used monomers possessing molecular weights greater than 700 g/mol. A main objective of this study was to toughen the vinyl ester while limiting plasticization by varying rubber reactivity and concentration. All modified samples experienced a significant increase in fracture toughness with some degree of plasticization, as shown by losses in modulus and glass transition temperature (T_g). Epoxy terminated rubber (ETBN) yielded a higher toughness than vinyl terminated rubber (VTBN) due to the difference in rubber particle formation and resulting morphology. Chemical linkage of VTBN to the vinyl ester matrix hindered complete phase separation, but helped the retention of mechanical properties when compared to ETBN.     

橡胶增韧环氧灌封料的研究

以液体羧基丁腈橡胶、液体聚硫橡胶为增韧剂制成环氧树脂灌封料,通过冲击强度、弯曲强度和拉伸剪切强度评价增韧环氧树脂灌封料的效果。实验结果表明,加入增韧剂的灌封料韧性与对照组相比均有不同程度的提高;液体聚硫橡胶增韧的环氧树脂灌封料表现出较好的抗冲击性能和抗弯曲性能;液体羧基丁腈橡胶增韧的环氧树脂灌封料表现出较好的拉伸剪切性能。     

A novel hybrid linear–hyperbranched poly(butylene adipate) copolymer as an epoxy resin modifier with toughening effect

A study was carried out on the effect of a hybrid linear–hyperbranched poly(butylene adipate) copolymer on the properties of a commercial epoxy resin. First, the synthesis of the hyperbranched systems was optimized. These systems were obtained by reacting linear oligomers with 1,1,1‐tris(hydroxymethyl)propane used as branching agent and varying the reaction times from 16 to 44 h. The synthesized samples were characterized through matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, differential scanning calorimetry and thermogravimetric analysis. Results showed that for reaction times of 30 h a highly branched system, namely 5HB30, was obtained. This system was chosen as toughening agent for a commercial high‐performance epoxy resin. A kinetics analysis of epoxy/5HB30 blends indicated that the hyperbranched system had no accelerator or catalytic effect on the crosslinking reaction in the resin. Furthermore, it was demonstrated that 5HB30 acted as an excellent toughening agent, increasing significantly impact resistance up to 90% with respect to neat epoxy resin. The toughness behaviours of epoxy‐based blends were explained by investigating the fracture surface after impact tests through scanning electron microscopy before and after solvent etching. It was observed that the globular‐like hyperbranch‐rich domains, dispersed throughout the continuous epoxy resin, were able to absorb the impact energy without affecting thermal stability. © 2015 Society of Chemical Industry     

双酚A及端羧基丁腈橡胶对环氧树脂的增韧作用

以2-乙基-4-甲基咪唑为固化剂,分别以端羧基丁腈橡胶(CTBN)、CTBN/双酚A(BPA)或BPA为增韧剂增韧环氧树脂,研究了环氧树脂增韧体系的微观形貌和力学性能,考察了不同混料方式对CTBN增韧环氧树脂性能的影响。结果表明:CTBN增韧环氧树脂能使其固化物的冲击韧性有所提高,但其他力学性能降低;采用环氧树脂先与其进行预聚反应再经固化剂固化的方法能提高CTBN对环氧树脂的增韧效果;用CTBN/BPA为增韧剂不仅可以大幅度提高材料的冲击强度和扯断伸长率,而且可以提高弯曲强度与模量,克服了CTBN单一增韧导致材料强度下降的不足。BPA的加入可使环氧树脂固化物体系的弯曲强度、冲击强度和扯断伸长率有较大幅度的提高。