Toughened epoxy adhesive modified with acrylate based liquid rubber

The adhesive and mechanical properties of epoxy resins modified with carboxyl terminated poly(2‐ethylhexyl acrylate) (CTPEHA) liquid rubber have been investigated as a function of the concentration of liquid rubber. CTPEHA was synthesized by the bulk polymerization technique. CTPEHA oligomer was prereacted with the epoxy and the modified epoxy networks were made by curing with an ambient temperature curing agent. The modified epoxy networks were evaluated with respect to their adhesive and mechanical properties. The optimum properties were obtained at about 10–15 phr (phr stands for parts per hundred parts of epoxy resin) concentration of modifier. Fracture surface analysis by optical microscopy (OM) indicates the presence of two phase microstructures. © 2000 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     

Mechanical properties and morphology of epoxidized soyabean‐oil‐modified epoxy resin

Epoxidized soyabean oil (ESO) has been used to toughen epoxy resin cured with an ambient temperature hardener. The ESO was prepolymerized before blending with epoxy resin to obtain modified networks having various concentrations of ESO. The modified networks were also made by blending the ESO with epoxy resin by a one‐stage process. All the modified networks were characterized for their thermal, flexural and impact properties, and compared to the parent epoxy network. The optimum properties were obtained at 20 parts per hundred grams of resin (phr) of ESO. The impact behaviour is explained in terms of morphology observed by scanning electron microscopy. © 2001 Society of Chemical Industry     

Use of acrylate‐based liquid rubbers as toughening agents and adhesive property modifiers of epoxy resin

Carboxyl‐randomized poly(2‐ethyl hexyl acrylate) (CRPEHA) and epoxy‐randomized poly(2‐ethylhexyl acrylate) (ERPEHA) were synthesized by solution polymerization technique in the form of liquid rubbers. The liquid rubbers were characterized by IR and ¹H‐NMR spectroscopic analysis, nonaqueous titration, and GPC. The liquid rubbers were pre‐reacted with the epoxy resin and the modified epoxy networks were made by curing with an ambient temperature curing agent. The modified epoxy networks containing different concentrations of CRPEHA (A‐1) and ERPEHA (B‐1) were evaluated with respect to their thermal and impact properties. The optimum properties were obtained at 10‐phr concentration of a (1 : 1) mixture of CRPEHA and ERPEHA. Fracture surface analysis by scanning electron microcopy indicated the presence of a two‐phase microstructure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3814–3821, 2004     

Study of impact properties and morphology of 4,4′‐diaminodiphenyl methane cured epoxy resin toughened with acrylate‐based liquid rubbers

Randomized carboxyl poly(2‐ethylhexyl acrylate) (A‐1) and randomized epoxy poly(2‐ethylhexyl acrylate) (B‐1) rubbers were synthesized in the form of liquid rubber by a solution polymerization technique. The liquid rubbers A‐1 and B‐1 were characterized by ¹H NMR and IR spectroscopic analysis, non‐aqueous titration, viscosity measurements and gel permeation chromatography. The liquid rubbers A‐1 (M?_n = 3900 g mol^?1), B‐1 (M?_n = 4100 g mol^?1) and a (1:1) mixture of A‐1 and B‐1 were pre‐reacted with epoxy resin separately and the modified epoxy networks were made by curing with high temperature curing agent. The modified epoxy networks were evaluated by unnotched Izod impact testing. The morphology and toughening behaviour were analysed by scanning electron microscopy. Optimum properties were obtained with the mixture of A‐1 and B‐1. Copyright © 2003 Society of Chemical Industry     

Toughening of epoxy resin by modification with 2‐ethylhexyl acrylate–acrylic acid copolymers

2‐Ethylhexyl acrylate–acrylic acid copolymers, ie carboxyl randomized poly(2‐ethylhexyl acrylate) (CRPEHA) (LR‐1 to LR‐6), with different molecular weights and functionality were synthesized. The liquid rubbers were characterized by FTIR spectroscopic analysis, non‐aqueous titration, vapour pressure osmometry (VPO) and viscosity measurements. All the liquid rubbers were reacted with the epoxy resin in 10:100 weight ratio using triphenyl phosphine as a catalyst. The modified epoxy networks were made by reacting the homogeneous prereacted resin with an ambient temperature hardener, triethylene tetramine (HY 951). The effect of the molecular weight and functionality of the liquid rubbers on the thermal and impact properties of the modified networks was investigated. © 2000 Society of Chemical Industry     

Novel dibutyltin oxide‐tributyl phosphate condensate as accelerator for the curing of the epoxy resin/4,4′‐diamino diphenyl sulfone system. II. Toughening of the resin with hydroxyl‐terminated poly(tetramethylene) glycols

When a crystalline Bu₂SnO‐Bu₃PO₄ condensate was used as a catalyst for the curing of the Epon 828/DDS system, the addition of hydroxyl group to epoxy group took place. On the basis of this reaction, direct employment of poly(tetramethylene) glycols (PTMG) as toughener for the epoxy resin system was successful. Morphology of the modified resin depended on the molecular weight and the concentration of PTMG. With the incorporation of a small amount of PTMG, the critical fracture energy of the cured resin was improved greatly, while the flexural strength and the modulus were less influenced. A slight enhancement in glass transition temperature (T_g) of the modified resin was found up to the PTMG concentration of 5 phr; further increase of the PTMG concentration caused a significant lowering of T_g. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1237–1242, 2001     

Mechanical and tribological properties of epoxy modified by liquid carboxyl terminated poly(butadiene-co-acrylonitrile) rubber

Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin was modified using liquid carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) rubber. The liquid CTBN contents used ranged from 2.5 to 20 parts per hundred parts of resin (phr). Mechanical properties of the modified resins were evaluated and the microstructures of the fracture surfaces were examined using SEM technique. The changes in storage modulus and the glass transition temperature were also evaluated using dynamic mechanical analysis (DMA). The tribological tests were performed using a ball-on-disc tribometer. The worn surfaces and the ball counter-mates after tribological tests were investigated using optical microscope technique. The results revealed the influence of liquid CTBN content on mechanical and tribological properties, and also microstructure of the modified epoxy resins. Impact resistance increased whereas the storage modulus and the hardness decreased when the CTBN rubber was introduced to the epoxy network. The coefficient of friction of the CTBN-modified epoxy was lower than that of the neat epoxy. The CTBN content of lower than 10 phr was recommended for improving the wear resistance of epoxy resin. Changes in tribological properties of the CTBN-modified epoxy correspond well to those in mechanical changes, especially the toughness properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and evaluation of liquid amine‐terminated polybutadiene rubber and its role in epoxy toughening

Epoxy resin is widely used for coatings, adhesives, castings, electrical insulation materials, and other applications. However, unsolved problems still remain in its applications. The main problem is low toughness: cured epoxy resin is rather brittle, with poor resistance to the propagation of cracks derived from the internal stress generated by shrinkage in the cooling process from cure temperature to room temperature. The objective of this study was to improve the flexibility and toughness of diglycidyl ether of bisphenol A based epoxy resin with a liquid rubber. For this purpose, amine‐terminated polybutadiene (ATPB) was synthesized. The product was characterized by Fourier transform infrared and NMR spectroscopy and elemental analysis. ATPB‐modified epoxy networks were made by curing with an ambient‐temperature curing agent, triethylene tetramine. We varied the epoxy/liquid rubber compositions to study the effect of toughener concentration on the impact and thermal properties. Higher mechanical properties were obtained for epoxy resins toughened with 1 phr ATPB. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2446–2453, 2005     

Thermal decomposition kinetics of an epoxy resin with rubber‐modified curing agent

Thermal decomposition kinetics of diglycidyl ether of bisphenol A (DGEBA)/4,4′‐methylene dianiline (MDA) system with rubber‐modified MDA was studied by the methods of Ozawa, Kissinger, and Friedman, and the kinetic parameters were compared. The thermal decomposition data of the cured epoxy resin were analyzed by thermogravimetric analysis (TGA) at different heating rates. TG curves showed that the thermal decomposition of the epoxy system occurred in one stage regardless of rubber‐modified MDA content. The apparent activation energies for the DGEBA/MDA system with 10 phr of rubber‐modified MDA, as determined by the Ozawa, Kissinger, and Friedman methods, are 184, 182, and 222 kJ/mol, respectively. The thermal stability of the epoxy system increased with the increasing content of rubber‐modified MDA, which has four benzene rings with high thermal resistance due to the resonance structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 479–485, 2001     

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     

Toughened epoxy-liquid polybutadiene networks cured with anhydride with outstanding thermal and mechanical properties

Toughened epoxy systems cured with anhydride-based hardener were successfully prepared by incorporating nonpolar liquid polybutadiene (PB) previously functionalized with isocyanate groups (PBNCO). The NCO groups in PBNCO react with the hydroxyl and/or epoxy groups of the matrix forming a ER-PB-ER triblock copolymer. The block copolymer is evidenced by transmission electron microscopy (TEM). In fact the modified epoxy resin (ER) networks presented domains with cocontinuous-like morphology, composed by PB and ER phases in nanomeric dimensions. The effect of PBNCO on the curing process of ER was studied by rheometry. Also the resulting networks were characterized by mechanical and dynamic mechanical properties, differential scanning calorimetry, and TEM. By adding an amount of rubber as high as 20 phr, a great improvement of toughness (around 140%) and impact resistance as well as a good transparency were achieved without significantly affecting the modulus and stiffness. Also the glass transition temperature (Tg) increased around 10°C with the presence of 5 phr of PBNCO. Even with the addition of 20 phr of rubber, the Tg of the system was superior than that found for the neat epoxy network. The outstanding physic-mechanical performance is attributed to the peculiar morphology.     

Flexibility improvement of epoxy resin by chemical modification

Epoxy resin was chemically modified with carboxyl‐terminated poly(ethylene glycol) adipate (CTPEGA) and the modified epoxy networks were made by curing with an ambient‐temperature hardener. The modified epoxy networks containing various concentrations of CTPEGA were characterized for their tensile, flexural and impact properties. It was observed that the mechanical strength gradually decreases and the strain increases with increasing CTPEGA concentration. However, the toughness and impact strength gradually increase with increasing CTPEGA concentration, attain a maximum and then decrease. The optimum CTPEGA concentration was found to be 20 phr. Fracture surface analysis by scanning electron microscopy indicates massive plastic deformation in modified networks. Copyright © 2004 Society of Chemical Industry     

端异氰酸酯聚丁二烯液体橡胶初步表征及应用

用ＩＲ光谱和分子量变化初步表征端异氰酸酯聚丁二烯液体橡胶（ＩＴＰＢ）,用ＩＲ证明了ＩＴＲＢ改性环氧树脂Ｅ—４４化学键合作用的存在。ＩＴＲＢ改性环氧树脂抗冲击强度与剪切强度的结果表明ＩＴＲＢ最佳用量在２４份左右。ＩＴＲＢ在水力机械、电子灌封及建筑防水行业的优异使用性能展示了ＩＴＲＢ良好的应用前景     

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     

Mechanical properties and fracture behaviors of epoxy composites with phase‐separation formed liquid rubber and preformed powdered rubber nanoparticles: A comparative study

Epoxy composites filled with phase‐separation formed submicron liquid rubber (LR) and preformed nanoscale powdered rubber (PR) particles were prepared at different filler loading levels. The effect of filler loading and type on the rheological properties of liquid epoxy resin suspensions and the thermal and mechanical properties of the cured composites as well as the relative fracture behaviors are systematically investigated. Almost unchanged tensile yield strength of the cured epoxy/PR composites is observed in the tensile test compared with that of the neat epoxy; while the strength of the cured epoxy/LR composites shows a maximum value at ∼4.5 wt% and significantly decreases with increasing LR content. The glass transition temperature (T_g) of the cured PR/epoxy has shifted to the higher temperature in the dynamic mechanical thermal analysis compared with that of the cured pure epoxy and epoxy/LR composites. Furthermore, the presence of LR results in highly improved critical stress intensity factor (K_IC) of epoxy resin compared with the corresponding PR nanoparticles. In particular, the PR and LR particles at 9.2 wt% loading produce about 69 and 118% improvement in K_IC of the epoxy composites, respectively. The fracture surface and damage zone analysis demonstrate that these two types of rubber particles induce different degrees of local plastic deformation of matrix initiated by their debonding/cavitation, which was also quantified and correlated with the fracture toughness of the two epoxy/rubber systems. POLYM. COMPOS., 36:785–799, 2015. © 2014 Society of Plastics Engineers     

Relationship between viscoelastic properties and gelation in the epoxy/phenol‐novolac blend system with N‐benzylpyrazinium salt as a latent thermal catalyst

A study of viscoelastic properties and gelation in epoxy/phenol‐novolac blend system initiated with 1 wt % of N‐benzylpyrazinium hexafluoroantimonate (BPH) as a latent cationic thermal initiator was performed by analysis of rheological properties using a rheometer. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. In the relationship between viscoelastic properties and gelation of epoxy/phenol‐novolac blend system, the time of modulus crossover was dependent on high frequency and cure temperature. The activation energy (E_c) for crosslinking from rheometric analysis increased within the composition range of 20–40 wt % phenol‐novolac resin. The 40 wt % phenol‐novolac (N40) to epoxy resin showed the highest value in the blend system, due to the three‐dimensional crosslinking that can take place between hydroxyl groups within the phenol resin or epoxides within the epoxy resin involving polyaddition of the initiator with BPH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2299–2308, 2001     

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     

Curing kinetics and thermal properties of diglycidylether of bisphenol A with various diamines

To prepare a high‐performance epoxy, we synthesized three types of diamines {N,N′‐(4,4′‐diphenylether)‐bis(4‐aminophthalimide), 4,4′‐bis(p‐aminophenoxy)dibenzalphentaerythriol, and 2,2′‐bis[4‐(p‐aminobenzoyl)phenyl]propane} as epoxy curing agents with a two‐step reaction sequence. The structures of the synthesized diamines were confirmed with Fourier transform infrared and nuclear magnetic resonance spectroscopy. The curing kinetics and thermal stability of the cured epoxy resin with diglycidylether of bisphenol A were estimated with differential scanning calorimetry and thermogravimetric analysis under a nitrogen atmosphere. The kinetics parameters were determined with the Ozawa and Kissinger equations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 279–284, 2001