Synthesis and properties of urethane elastomer-modified epoxy resin having hydroxymethyl group

Synthesis and properties of urethane elastomer-modified epoxy resins were studied. The urethane elastomer-modified epoxy resins were synthesized by the reaction of a 4-cresol type epoxy compound having hydroxymethyl groups (EPCDA) with isocyanate prepolymer. The structure was identified by IR, ¹H NMR and GPC. These epoxy resins (EPCDATDI) were mixed with a commercial epoxy resin (DGEBA) in various ratios. The mixed epoxy resins were cured with a mixture of 4,4′-diaminodiphenylmethane and 3-phenylenediamine (molar ratio 6:4) as a hardener. The curing behaviour of these epoxy resins was studied by DSC. The higher the concentration of EPCDATDI, the higher the onset temperature and the smaller the rate constant (k) of the exothermic cure reaction were. It was considered that the ratio of hydroxymethyl group to epoxide group was very small and the molecular weight of EPCDATDI was large. Therefore, the accelerating effect of the hydroxymethyl group on the epoxide–amine reaction was cancelled by the retardant effect of increased molecular weight and viscosity, and decreased molecular motion. Toughness was estimated by Izod impact strength and fracture toughness (K_1C). On addition of 10 wt% EPCDATDI with low molecular weight (M?_n 6710, estimated by GPC using polystyrene standard samples), Izod impact strength and K_1C increased by 70% and 60%, respectively, compared with unmodified epoxy resin. Glass transition temperatures (T_g) for the cured epoxy resins mixed with EPCDATDI measured by dynamic mechanical spectrometry were the same as those of unmodified epoxy resin. The storage modulus (E′) at room temperature decreased with increasing concentration of EPCDATDI. Toughness and dynamic mechnical behaviour of cured epoxy resin systems were studied based on the morphology.     

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.     

CA型环氧树脂固化剂性能研究

用ＩＲ光谱表征了自制ＣＡ型环氧树脂固化剂的结构特点,测定了ＣＡ型固化剂的固化特性,固化树脂的性能和增塑效果。实验结果表明,ＣＡ型固化剂能使环氧树脂涂料在潮湿表面和带油表面上固化成膜,其固化的树脂具有良好的耐蚀性,冲击强度较二乙撑三胺固化的树脂有较大提高,同时也是一种较好的环氧树脂用增塑剂。     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

雷达天线罩应急快速修补胶的研究

对不同种类固化剂、增韧剂、稀释剂及其用量对环氧树脂性能的影响进行了考察,并对环氧树脂在不同温度、湿度下固化的性能进行了研究。结果表明,曼尼希改性胺在高湿条件下固化性能最佳;随着增韧剂A用量的增加,体系的剪切强度和剥离强度先增加后降低;稀释剂A的含量增大,体系的黏度下降,但粘接强度也随之下降。研制的胶黏剂室温剪切强度约20MPa、90度剥离强度为2～3．5kN／m,固化2h剪切强度就达4～10MPa,可用于雷达天线罩的快速修补及材料的结构粘接。     

Silica/poly(styrene-alt-maleic anhydride) hybrid particles as a reactive toughener for epoxy resin

Amino-modified silica nanoparticles (SiO₂─NH₂) were first prepared by hydrolytic condensation of tetraethyl orthosilicate and 3-aminopropylmethyldiethoxysilane. Then, organic–inorganic hybrid particles (SiO₂─SMA) were prepared by the amidation reaction between SiO₂─NH₂ and poly(styrene-alt-maleic anhydride) (SMA). Subsequently, SiO₂─SMA particles were employed for modifying bisphenol-A epoxy/anhydride thermoset. Compared with pure cured epoxy, the modified epoxy thermosets with only 1 wt % of SiO₂─SMA particles could achieve a simultaneous toughening and reinforcing performance. The tensile strength, impact strength, and fracture toughness of epoxy thermoset were increased by 14.1, 44.3, and 114.4%, respectively. Moreover, the modification also improved the thermal stability of epoxy thermosets, and the modulus and glass transition temperature of cured resin were not sacrificed. It can be attributed to the rigid structure of SiO₂, as well as the anhydride and carboxyl groups onto the surface of SiO₂─SMA particles participating in the epoxy curing reaction and effectively enhancing the crosslinking density of epoxy thermoset.     

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.     

Frontal curing of epoxy resins: Comparison of mechanical and thermal properties to batch-cured materials

The epoxy resin diglycidyl ether of bisphenol F (DGEBF) was cured by the aliphatic amine curing agent Epicure 3371 in a stoichiometric ratio both frontally and in a batch-cure schedule. Glass transition temperatures (T_g) were determined using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). DMA also was used for studying the storage modulus (E′) and tan delta (tan δ) of the cured samples. Tensile properties of epoxy samples were tested according to ASTM D638M-93. The properties of the frontally cured epoxy resin were found to be very close to that of batch-cured epoxy resin. Velocity of cure-front propagation was measured for both neat and filled epoxy. Rubber particles (ground tires) were used as a filler. The maximum percentage of filler in the epoxy resin allowing propagation was 30%. Because of convection, only descending fronts would propagate. Advantages and disadvantages of frontal curing of epoxy resins are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1209–1216, 1997     

An approach to chemical recycling of epoxy resin cured with amine using nitric acid

An approach to chemical recycling of epoxy resin was pursued. Bisphenol F type epoxy resin cured with 1,8-p-menthanediamine could be completely decomposed in nitric acid solution resulting from low corrosion resistance to nitric acid. Organic decomposed products of the resin with the highest yield were extracted from neutralized solution. The extract was repolymerized to prepare recycled resin, mixed with bisphenol F type epoxy resin and curing agent of phthalic anhydride. The mechanical properties of virgin resin and recycled resins were compared. It was surprising that the recycled resins were far superior to the virgin resin in strength. The results obtained from differential scanning calorimeter (DSC) showed that the glass transition temperature (T_g) of recycled resins was higher than that of virgin resin. The reason that they formed the better network structure was discussed.     

The Curing Behavior and Adhesion Strength of the Epoxidized Natural Rubber Modified Epoxy/Dicyandiamide System

The curing properties and adhesive strengths of the epoxidized natural rubber (ENR, 25 mole percent epoxidation) modified epoxy systems are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and lap shear strength (LSS) measurement. The results of DSC analyses indicate that the curing exotherm, the curing rate, the reaction order, and the glass transition temperature of the epoxy system are affected by the presence of reactive ENR. From SEM micrographs, it is obtained that a second spherical rubber phase is formed during cure and the particle size of the rubber phase is increased by increasing the curing temperature and the ENR content. The changes of the volume fraction of the rubber phase and the T_g of the cured systems indicate that the mutual dissolution between epoxy resin and ENR happens and which changes with the curing temperature and the ENR content. The LSS of adhesive joints prepared with the ENR modified adhesives are all lower than those of the unmodified epoxy system, and decrease with increasing the amount of ENR added because of the limited compatibility of the ENR with the epoxy matrix.     

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     

Novel cycloaliphatic epoxy resins. II. Curing reaction with BF3MEA and its cured properties

The BF₃MEA curing reaction and the cured properties of novel cycloaliphatic epoxy resins (CE-resins), which were derived from an octadienyl compound, were studied. Gelation time and the DSC scan of the CE resins, with BF₃MEA hardener, proved that the reactivity of the CE resins is intermediate among the reactivities of the conventional resins; it was found that the CE resins react faster than DGEBA, but slower than the conventional cycloaliphatic epoxy resins. The pot life of the CE- (III) resin with BF₃MEA hardener proved to be over 30 days at a temperature of 20°C. The thermal properties are affected by the amount of BF₃MEA used and the curing conditions. CE-(III) showed the highest HDT of over 200°C with 2–3 phr of BF₃MEA. The flexural properties of CE-(I) proved to be flexible and tough. CE-(II) exhibited the highest strength and elongation, while CE-(III) had the same flexural properties as DGEBA. Furthermore, the blending of CE-(II) with DGEBA produced greater flexural strength and greater elongation than each original resin had. The thermal stability at elevated temperature and the water resistance of the cured CE resins proved to be inferior to those of DGEBA and novolac epoxy resin, probably due to the use of BF₃MEA. These results suggest the CE resin will provide a new application for a one-component curing system for composites. © 1993 John Wiley & Sons, Inc.     

The effects of additives on curing properties,resin contents,and mechanical properties of graphite/epoxy composites

The effects of additives such as boron trifluride-monoethylene amine (BF₃MEA) and fumed silica in the TGDDM/DDS epoxy formulations on the curing properties, resin contents, and mechanical properties of their graphite/epoxy (Gr/Ep) composites were investigated. The addition of BF₃MEA increased the viscosity of resin as well as the resin contents of cured laminates because of its catalytic effect. Although the fumed silica was considered a thickening agent, it also acted like a co-catalyst with BF₃MEA. As the resin content of cured laminates was increased, the excess resin was likely to accumulate in the interlaminar region, which increased the interlaminar shear strength but decreased the flexure strength as well as the interlaminar fracture toughness value, G_IC.     

Preparation of epoxy-based insulator and optimization of its thermal property by Taguchi robust design method in double base propellant grain application

Taguchi method (orthogonal array, OA₉) was used to design an epoxy insulator by evaluating its glass transition temperature (T _g) for using in a double base (DB) propellant grain. In this design method, three epoxy resins based on diglycidylether bisphenol A (DGEBA), three polyamine curing agents and a DGEBA-based reactive diluent agent were used. The curing process of epoxy resins with polyamines was studied by Fourier transform infrared spectroscopy. The results showed that the curing process was completed at room temperature. The effects of four parameters including resin type, curing agent type, curing agent concentration and diluent quantity were investigated to design a resin formulation with a highest T _g after curing. The obtained results were quantitatively evaluated by the analysis of variance (ANOVA). The results of ANOVA showed that the highest T _g of 86.0 ± 9.0 °C was obtained for the optimum formulation of MANA POX-95 as epoxy resin, H-30 as curing agent and 52 phr H-30. The T _g measured by the experiment was 78.0 ± 0.9 °C. In addition, the single lap shear strength (adhesion strength) of the optimized insulator was measured at 13.66 ± 1.02 MPa. Pull-off test performed on the surface of DB propellant resulted a 1.935 ± 0.003 MPa adhesion strength.     

Curing and Morphology of BPA Epoxy Resin/LC Epoxy Resin PEPEB Composites

Liquid crystalline epoxy resin (LC epoxy resin) – p-phenylene di{4-[2-(2,3-epoxypropyl)ethoxy]benzoate} (PEPEB) was synthesized. The mixture of PEPEB with bisphenol-A epoxy resin (BPAER) was cured with a curing agent 4,4-diamino-diphenylmethane (DDM). The curing process and thermal behavior of this system were investigated by differential scanning calorimeter (DSC) and torsional braid analysis (TBA). The morphological structure was measured by polarizing optical microscope (POM) and scanning electron microscope (SEM). The results show that the initial curing temperature Ticu (gel point) of this system is 68.1°C, curing peak temperature T _pcu is 102.5°C, and the disposal temperature T _fcu is 177.6°C. LC structure was fixed in the cured epoxy resin system. The curing kinetics was investigated by dynamic DSC. Results showed that the curing reaction activation energy of BEPEB/BPAER/DDM system is 22.413 kJ/mol. The impact strength is increased 2.3 times, and temperature of mechanical loss peak is increased to 23°C than the common bisphenol-A epoxy resin, when the weight ratio of BEPEB with BPAER is 6 100.     

Silyl-Crosslinked Urethane Elastomer Modifying Epoxy Resin: I. Morphological Studies

Silyl-crosslinked urethane elastomer modifying epoxy resin has drawn much interest. Here triethoxysilyl-terminated polycaprolactone elastomer (PCL-TESi) modifying diglycidylether of bisphenol A epoxy resins (DGEBA) system was chosen; then the effect of the type of curing agent on the phase structure of the studied system was investigated. The modified systems with different phase structures were obtained by varying the formulations of the curing agents. It was experimentally shown that the crosslinked density was greatly increased by the addition of an aminosilane curing agent (KBE-9103). And the SEM and TEM analysis of the cured system showed that the addition of KBE-9103 increased the compatibility between the PCL-TESi and DGEBA, but decreased the ductility of the systems. The TEM results indicated that the addition of too much of the KBE-9103 made the resulting silicone particles coagulate with each other. The state of phase separation from the TEM in the cured system was explained theoretically. These considerations would serve the deeper studies of the mechanism of silyl-crosslinked urethane elastomer modifying epoxy resin in the future.     

Preparation and mechanical properties of epoxy/diamond nanocomposites

Nanodiamond (ND) has recently attracted much attention for its outstanding mechanical and other interesting properties. Surface functionalization of ND is necessary for applications in polymers. In this study, ND particles were functionalized with amine by covalent linking of triethylene tetramine, and further grafted with epoxy which was cured with amine curing agent. The particle dispersion and mechanical properties of epoxy/ND nanocomposites were evaluated. Both fracture toughness and storage modulus of epoxy resin were significantly improved with a low loading of ND‐NH₂ particles. The morphological structure of the epoxy/ND nanocomposites was examined, and toughening mechanism was explored. POLYM. COMPOS., 35:2144–2149, 2014. © 2014 Society of Plastics Engineers     

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     

Preparation and properties of waterborne polyurethane/epoxy resin composite coating from anionic terpene-based polyol dispersion

An anionic polyol (T-PABA) dispersion was prepared by modifying terpene-based epoxy resin with para-aminobenzoic acid. Then T-PABA dispersion was crosslinked with a hexamethylene diisocyanate (HDI) tripolymer to prepare waterborne polyurethane/epoxy resin composite coating. The rheological properties and particle size distribution of the composite system were characterized by rotary rheometer and laser particle size analyzer. The crosslinked composite product has good thermal resistant properties, with glass-transition temperatures (T_g) about 40% and 50% weight loss temperatures (T_d) in the range of 400–420. The smooth and transparent film obtained from the composite product has good flexibility, adhesion, impact strength, antifouling and blocking resistance properties. The impact strength, pencil hardness, water-resistant and thermal-resistant properties of the composite products increased with the molar ratio of isocyanate group to active hydrogen of T-PABA.     

新型环氧树脂增韧稀释剂的性能研究

采用国产669环氧稀释剂与聚氨酯预聚物反应合成了含有端环氧基聚醚氨酯的环氧树脂增韧稀释剂(U669)。将该化合物与环氧树脂(E51)共混,并分别采用氰乙基化己二胺和593#固化,通过力学性能测试,研究了U669含量对固化物性能的影响,并采用扫描电镜观察了断面微观结构。结果发现:其固化物具有海岛结构;2种固化体系的剪切强度在E51/U669质量比为60/40时达到极值,分别为21.91MPa和16.21MPa;采用593#作固化剂,在E51/U669质量比为80/20时,共混固化物的拉伸强度和弯曲强度达到最大值62.63MPa和97.37MPa;采用氰乙基化己二胺固化的体系的断裂伸长率和冲击性较593#固化体系好,其最大断裂伸长率达120.98%,当U669质量分数大于50%时,固化物具有弹性体的特征。