Curing behaviour of syndiotactic polystyrene–epoxy blends: 1. Kinetics of curing and phase separation process

The modification of the curing behaviour and the phase separation process for an epoxy resin blended with a crystalline thermoplastic was investigated in the case of the diglycidylether of bisphenol‐A (DGEBA)/4,4′‐methylene bis(3‐chloro‐2,6‐diethylaniline) (MCDEA) blended with syndiotactic polystyrene (sPS) and cured at 220 °C. Phase separation taking place during curing of the blend was investigated by differential scanning calorimetry (DSC) and optical microscopy in order to get a better understanding of the complex interactions between cure kinetics of epoxy matrix and crystallisation of sPS, both influenced by blend composition. Results suggested that phase separation and crystallisation of sPS occurred at almost similar times, with phase separation just being ahead of crystallisation. DSC and near‐infrared measurements were used for the determination of the cure kinetics. Slow delays on the cure reactions were observed during the first minutes for the sPS‐containing blends compared with the neat DGEBA/MCDEA system but, after some time, the reaction rate became faster for the blends than for the neat matrix. Phase separation occurring in the mixtures may explain this particular phenomenon. Copyright © 2004 Society of Chemical Industry     

Azo initiator selection to control the curing order in dimethacrylate/epoxy interpenetrating polymer networks

Differential Scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) spectroscopic studies have been undertaken of the cure of interpenetrating polymer networks (IPNs) formed with imidazole‐cured diglycidyl ether bisphenol‐A (DGEBA) and with either diethoxylated bisphenol‐A dimethacrylate (DEBPADM) or bisphenol‐A diglycidyl dimethacrylate (bisGMA), polymerized by a range of azo initiators (AIBN64, VAZ088, VR110 and AZO168). Due to the differing decomposition rates of the azo initiators, the neat dimethacrylate resin either cured faster than (with AIBN64 and VAZO88), or similar to (VR110), or slower than (AZO168), the neat epoxy resin. In the neat DGEBA/1‐methyl imidazole (1‐MeI), DEBPADM/AIBN64, DEBPADM/VAZO88 and DEBPADM/VR110 resins, close to full cure was achieved. For the neat, high‐temperature DEBPADM/AZO168 resin, full cure was not attained, possibly due to the compromise between using a high enough temperature for azo decomposition while avoiding depolymerization or decomposition of the methacrylate polymer. IPN cure studies showed that, by appropriate initiator selection, it was possible to interchange the order of cure of the components within the IPN so that either the dimethacrylate or epoxy cured first. In the isothermal cure of the 50:50 DEBPADM/AIBN64:DGEBA/1‐Mel IPN system, the cure rate of both species was less than in the parent resins, due to a dilution effect. For this system, the dimethacrylate cured first and to high conversion, due to plasticization by the unreacted epoxy, but the subsequent cure of the more slowly polymerizing epoxy component was restricted by the high crosslink density developed in the IPN. After post‐curing, however, high conversion of both reactive groups was observed and the fully cured IPN exhibited a single high‐temperature T_g, close to the T_g values of the parent resins. In the higher‐temperature, isothermal cure of the 50:50 DEBPADM/VR110:DGEBA/1‐Mel IPN system, the reactive groups cured at a similar rate and so the final conversions of both groups were restricted, while in the 50:50 DEBPADM/AZO168:DGEBA/1‐Mel system it was the epoxy which cured first. Both of these higher‐temperature azo‐initiated IPN systems exhibited single T_gs, indicating a single‐phase structure; however, the T_gs are significantly lower than expected, due to plasticization by residual methacrylate monomer and/or degradation products resulting from the high cure temperature. Copyright © 2004 Society of Chemical Industry     

Rubber modified epoxy resin. II: Phase separation behavior

DGEBA (diglycidyl ether of bisphenol A)–ATBN (amine terminated butadiene acrylonitrile copolymer) blends exhibited upper critical solution temperature (UCST) behavior. Triethylene tetramine (TETA) was introduced as an amine curing agent of epoxy. The real-time phase separation behavior of ATBN-added epoxy system during cure was investigated using laser light scattering. SEM (scanning electron microscopy) and optical microscopy were also employed to observe the morphology of the epoxy blends. Since the DGEBA–ATBN blends showed UCST behavior, the degree of phase separation when cured at low temperature was higher than that when cured at high temperature. The domain correlation length increased as the curing temperature was lowered. Dynamic mechanical analysis (DMA) results indicated that the phase inversion occurred above 20 wt% of ATBN composition.     

Cure kinetics of epoxy resin and aromatic diamines

The kinetics of curing reaction of a diglycidyl ether of a bisphenol‐A based epoxy (DGEBA) with 4,4′‐diaminostillbene (DAS) and 4,4′‐diaminoazobenzene (DAAB) as curing agents are studied by differential scanning calorimetery (DSC) using the isothermal technique. The experimental data show that the cure reaction is autocatalytic in nature, and all kinetic parameters of the curing reaction are determined using a semiempirical equation. The reaction of DGEBA with DAS is faster than that with DAAB under the same conditions and the activation energies of both systems are higher than those reported for other aromatic diamines. With increasing isothermal temperature and concentration of curing agents the rate constants are increased by the increasing of probability collisions between epoxide and primary amine groups while the activation energies remain constant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1049–1056, 2004     

Effect of curing order on the curing kinetics and morphology of bisGMA/DGEBA interpenetrating polymer networks

The curing kinetics and morphology of an interpenetrating polymer network (IPN) formed from an epoxy resin (DGEBA) cured by an imidazole (1‐MeI) and a dimethacrylate resin (bisGMA), cured by low‐ and high‐temperature peroxide initiators (TBPEH and DHPB, respectively) have been studied by temperature‐ramping DSC, isothermal near‐infrared (NIR), DMTA and small‐angle neutron scattering (SANS). bisGMA and DGEBA are polar and chemically similar thermosetting resins which should enhance the miscibility of their IPNs. The phase structure was controlled by varying the curing procedure: the order of gelation of the components is dependent on the choice of low‐ and high‐temperature initiators for bisGMA and this affects the morphology formation. In the cure of the bisGMA/TBPEH:DGEBA/1‐MeI system, the dimethacrylate cures first. For isothermal cure studies at 80 °C, the final conversion of the epoxy is reduced by high crosslinking of the methacrylate groups in the IPN causing vitrification before full cure. The dimethacrylate conversion is enhanced due to plasticisation with unreacted DGEBA, and its cure rate is increased due to accelerated decomposition of TBPEH initiator by 1‐MeI. SANS revealed that phase separation occurs in these IPNs with domains on the scale of 6–7 nm. In the cure of the bisGMA/DHBP:DGEBA/1‐MeI system, the epoxy cures at a similar rate to that of the methacrylate groups. For isothermal cure studies at 80 °C, similar final conversions of the epoxy have been observed except for the 75:25 IPN. The cure rate of the methacrylate groups in the IPN is increased also due to accelerated decomposition of DHBP initiator by 1‐MeI, and the extent of accelerated decomposition for DHBP is stronger than that in the TBPEH‐based systems. SANS studies revealed that this system is more homogeneous due to the rapid formation of the dimethacrylate gel in the presence of the preformed epoxy network which interlocks the networks at low degrees of methacrylate conversion. Copyright © 2006 Society of Chemical Industry     

Phase separation and rheological behavior during curing of an epoxy resin modified with syndiotactic polystyrene

The phase separation and crystallization processes occurring in a semicrystalline thermoplastic‐(epoxy/amine) system were studied by using dynamic oscillatory rheometry and differential scanning calorimetry (DSC). Moreover, a transmission optical microscope (TOM) equipped with a hot stage was used to get a direct representation of the obtained morphologies at different times during the phase separation and crystallization processes. The morphology of the cured samples was additionally studied by atomic force microscopy (AFM). The selected thermoset system was diglicydylether of bisphenol‐A (DGEBA) cured with 4,4′‐methylene bis (3‐chloro‐2,6‐diethylaniline) (MCDEA) and modified with syndiotactic polystyrene (sPS). In the initially miscible semicrystalline thermoplastic/thermoset system, phase separation is induced by the curing reaction (reaction‐induced phase separation [RIPS]) and by crystallization of the thermoplastic (crystallization induced phase separation [CIPS]). Both phenomena take place almost at the same curing time and both have strong influence on the morphology of cured samples. POLYM. ENG. SCI. 45:303–313, 2005. © 2005 Society of Plastics Engineers.     

Study on curing kinetics and curing mechanism of epoxy resin based on diglycidyl ether of bisphenol a and melamine phosphate

The curing kinetics of the diglycidyl ether of bisphenol A/melamine phosphate (DGEBA/MP) was analyzed by the DSC technique. The Kissinger and Flynn–Wall–Ozawa methods were applied to determine the dynamic kinetics of the DGEBA/MP system. The activation energies obtained by these two methods were 83.9 and 85.6 kJ/mol, respectively. An autocatalytic equation was applied to determine the isothermal curing kinetics of the DGEBA/MP system. The DGEBA/MP system exhibits autocatalytic behavior in the isothermal curing procedure, whose kinetics fits well with the autocatalytic mechanism. The obtained isothermal curing activation energy of the DGEBA/MP system was 110.0 kJ/mol. The curing mechanism of DGEBA with melamine phosphate was investigated using FTIR, ¹³C solid‐state NMR, and ³¹P solid‐state NMR. It involved an epoxide–amine reaction, etherification of phosphoric acid and epoxy, dehydration, and thermal oxidation of the hydroxyl group of the DGEBA/MP system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 892–900, 2004     

Processing and chemorheology of epoxy resins and their blends with dendritic hyperbranched polymers

Toughened epoxy systems have found increasing applications in automotive, aerospace, and electronic packaging industries. The present article reported work done for elucidation of gelation and vitrification for various epoxy systems and their blends with dendritic hyperbranched polymers (HBPs) having epoxy and hydroxyl functionality. Gel time was found to increase with increasing functionality from diglycidyl ether of bisphenol A (DGEBA) to tetraglycidyl diaminodiphenyl methane (TGDDM). The vitrification point was clearly identified from rheological experiments for triglycidyl p‐amino phenol (TGAP) and TGDDM. In the case of DGEBA a clear display of vitrification was not observed. TGDDM underwent vitrification sooner than did TGAP. Hydroxyl‐functionalized HBP reduced the gel time of the blends because of the accelerating effect of –OH groups to the epoxy curing reaction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1604–1610, 2004     

Polymerization of epoxy resins initiated by metal complexes

BACKGROUND: Processing parameters and material properties of epoxy resins can be vastly influenced by choice of curing agent. In this work, metal complexes were investigated as initiators for anionic and cationic epoxide polymerization. Systems for thermally induced and electron beam‐induced curing are described. RESULTS: Zinc or cobalt imidazole complexes of the type [M(imidazole)₂(anion)₂] are efficient initiators for anionic polymerization of glycidyl‐based epoxy resins. The complexes can be employed to prepare tailored resin systems ranging from fast curing systems at slightly elevated temperatures to systems with very high thermal latencies curable at temperatures far above 150 °C. Silver complexes [Ag(L)_n]SbF₆ (L = crown ether or alkene) are highly efficient initiators for cationic curing and low initiator contents of around 1% are sufficient to reach high degrees of crosslinking. The complexes are excellent initiators for both thermally induced and electron beam‐induced polymerizations. CONCLUSION: Metal complexes are powerful initiators for the homopolymerization of epoxy resins and can be designed not only for anionic and cationic polymerization but also for thermal and radiation curing. Based on this study and additional work, a library can be compiled which allows retrieval of optimized metal–ligand–anion combinations and adjustment of the initiators to the respective processing and material demands. Copyright © 2009 Society of Chemical Industry     

Design of morphology in PMMA‐modified epoxy resins by control of curing conditions. I. Phase behavior

Rheokinetic and phase separation behavior of diglycidylether of bisphenol‐A–4,4′‐diaminodiphenyl methane epoxy mixtures, modified with a constant amount (15 wt %) of poly(methyl methacrylate) (PMMA), have been investigated. Stoichiometric epoxy/amine mixtures precured at 80°C several times presented various levels of miscibility. Differential scanning calorimetry (DSC) and dynamic mechanic thermal analysis were used for rheokinetic studies of curing and also for testing the thermal behavior of the fully cured mixtures. Phase separation, through curing, was simultaneously studied by transmission optical microscopy and DSC, showing an excellent correlation between the results obtained with both techniques. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 772–780, 1999     

Transparent multiphasic polystyrene/epoxy blends

Blends of polystyrene (PS) with an epoxy monomer (DGEBA) and a tertiary amine (BDMA), were initially miscible at 120°C but phase‐separated at very low conversions in the course of polymerization. Although there was a significant difference between the refractive indices of polystyrene and the DGEBA/BDMA solution, the refractive index of the epoxy network increased in the course of polymerization, attaining a value close to that of PS at complete conversion. A sharp decrease of the light transmittance was observed at the cloud‐point, observed at very low conversions. However, the continuous increase of the refractive index of the epoxy phase with conversion produced an approximate matching of both refractive indices, leading to transparent materials at complete conversion. Morphologies generated by reaction‐induced phase separation depended on the molar mass distribution of polystyrene and its mass fraction in the blend. For a PS with a high value of the mass‐average molar mass (M_w), it was possible to generate a dispersion of PS particles in the epoxy matrix (blends containing 5 wt% PS), phase‐inverted morphologies (blends containing 15 wt% PS) and double‐phase morphologies (blends with 10 wt% PS). Therefore, PS/DGEBA/BDMA blends could be used to obtain transparent epoxy coatings toughened by polystyrene particles or transparent polystyrene parts reinforced by a dispersion of epoxy particles.     

Reactive blends of epoxy resin (DGEBA) crosslinked by anionically polymerized polycaprolactam: Process of epoxy cure and kinetics of decomposition

The curing reactions, kinetics, morphology, and thermal stability of the reactive blends of diglycidyl ether of bisphenol‐A (DGEBA) and polycaprolactam were studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis. DSC studies showed that the heat of reaction (ΔH) increased when the DGEBA content was increased from 50 to 80 wt % and increased drastically above 70 wt % DGEBA content because of an increase in the extent of crosslinking. The activation energy and pre‐exponential factor of cure reactions increased drastically with an increase in the DGEBA content above 70 wt % because of a drastic increase in crosslink density. The extent of curing reaction of polycaprolactam with DGEBA is dependent on the blend composition. The nucleophilic attack on oxirane ring by amide nitrogen of polycaprolactam is a dominant curing reaction in low DGEBA compositions, and another type of curing reaction with relatively large activation energy and pre‐exponential factor also occurred, which becomes dominant when the DGEBA content reaches above 70 wt %. FTIR studies also revealed that two types of reactions do exist during the curing of polycaprolactam with DGEBA. It was observed during SEM studies that the reactive blends show multiphase system and on increasing the DGEBA content from 50 to 80 wt %, the mixing of the two phases increased. The reactive blend Ep₈₀Ca₂₀ with 80 wt % DGEBA content exhibits a single‐phase system because of better mixing of the two phases. The results of thermogravimetric analysis also indicate that the initial degradation temperature (T_i), activation energy (E), and pre‐exponential factor (Z) increased with increasing DGEBA content from 50 to 80 wt % in the reactive blends and increased drastically above 70 wt % DGEBA content due to the higher crosslink density. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 687–697, 2004     

Polymerization‐induced bimodal phase separation in a rubber‐modified epoxy system

The bimodal phase separation process of a rubber‐modified epoxy system, consisting of diglycidyl ether of bisphenol A (DGEBA), and a hydroxyl‐terminated butadiene–acrylonitrile random copolymer (HTBN), during curing with tetrahydro‐phthalic anhydride was studied by time‐resolved small‐angle light scattering (TRSALS), differential scanning calorimetry (DSC), and digital image analysis (DIA). The HTBN/DGEBA mixture reveals an upper critical solution temperature (UCST). At higher curing temperatures, double‐peak structure from the matrix was investigated by TRSALS and confirmed by DIA. The special two characteristic size distribution behavior was explained qualitatively by nucleation growth coupled with spinodal decomposition (NGCSD) and the competition between phase separation and polymerization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 59–67, 1999     

Dielectric monitoring of curing of liquid oligomer‐modified epoxy matrices

Dielectric measurements were performed in ‘real‐time’ at several temperatures to follow polymerization reactions on blends of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin with 4, 4′‐diaminodiphenylmethane (DDM) hardener and different amounts of polyoxypropylenetriamine (POPTA) oligomer. These systems exhibit phase separation induced by molar mass increasing through curing of the resin. Monitoring of phase separation and vitrification (related to the α‐relaxation) was performed by this technique. The results are compared with those for the unmodified resin–hardener mixture. The change of the main α‐relaxation with cure time, cure temperature, and amount of modifier was measured for the mixtures. This change of the main relaxation through curing in the frequency domain was indicative of the cure reaction advancement, because of its dependence on the viscosity of the medium. The change of the ionic conductivity during curing was also analysed, showing its dependence upon cure temperature. © 2001 Society of Chemical Industry     

An epoxy‐ended hyperbranched polymer as a new modifier for toughening and reinforcing in epoxy resin

A new epoxy‐ended hyperbranched polyether (HBPEE) with aromatic skeletons was synthesized through one‐step proton transfer polymerization. The structure of HBPEE was confirmed by Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance (NMR) measurements. It was proved to be one high efficient modifier in toughening and reinforcing epoxy matrix. In particular, unlike most other hyperbranched modifiers, the glass transition temperature (T_g) was also increased. Compared with the neat DGEBA, the hybrid curing systems showed excellent balanced mechanical properties at 5 wt % HBPEE loading. The great improvements were attributed to the increased cross‐linking density, rigid skeletons, and the molecule‐scale cavities brought by the reactive HBPEE, which were confirmed by dynamical mechanical analysis (DMA) and thermal mechanical analysis (TMA). Furthermore, because of the reactivity of HBPEE, the hybrids inclined to form a homogenous system after the curing. DMA and scanning electron microscopy (SEM) results revealed that no phase separation occurred in the DGEBA/HBPEE hybrids after the introduction of reactive HBPEE. SEM also confirmed that the addition of HBPEE could enhance the toughness of epoxy materials as evident from fibril formation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1064‐1073, 2013     

Morphology of epoxy resin modified with silyl‐crosslinked urethane elastomer

Silyl‐crosslinked urethane elastomer modifying epoxy resin has drawn much interest. Here the triethoxysilyl‐terminated polycaprolactone elastomer (PCL‐TESi) modifying diglycidylether of bisphenol A epoxy resins (DGEBA) system was chosen, and then the effect of the type of curing agent on the phase structure of the studied epoxy resin system was investigated. The modified systems were obtained with different phase structures by varying the formulations of the curing agent. It was experimentally shown that with the addition of aminosilane (KBE‐9103), the crosslinked density was greatly increased. The cured system also showed from SEM and TEM analysis that addition of KBE‐9103 increased the compatibility between the PCL‐TESi and DGEBA, which made the ductility of the system decrease, but also indicated from TEM that addition of much KBE‐9103 made the reacted silicone particles coagulate each other. The state of phase separation from TEM in the cured system was theoretically explained. These would serve the deeper studies of the mechanism of silyl‐crosslinked urethane elastomer modifying epoxy resin in the future. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 611–619, 2005     

Toughening of epoxy resin systems using low‐viscosity additives

This study has evaluated three low‐viscosity epoxy additives as potential tougheners for two epoxy resin systems. The systems used were a lower‐reactive resin based upon the diglycidyl ether of bisphenol A (DGEBA) and the amine hardener diethyltoluene diamine, while the second epoxy resin was based upon tetraglycidyl methylene dianiline (TGDDM) and a cycloaliphatic diamine hardener. The additives evaluated as potential tougheners were an epoxy‐terminated aliphatic polyester hyperbranched polymer, a carboxy‐terminated butadiene rubber and an aminopropyl‐terminated siloxane. This work has shown that epoxy‐terminated hyperbranched polyesters can be used effectively to toughen the lower cross‐linked epoxy resins, i.e. the DGEBA‐based systems, with the main advantage being that they have minimal effect upon processing parameters such as viscosity and the gel time, while improving the fracture properties by about 54 % at a level of 15 wt% of additive and little effect upon the T_g. This result was attributed to the phase‐separation process producing a multi‐phase particulate morphology able to initiate particle cavitation with little residual epoxy resin dissolved in the continuous epoxy matrix remaining after cure. The rubber additive was found to impart similar levels of toughness improvement but was achieved with a 10–20 °C decrease in the T_g and a 30 % increase in initial viscosity. The siloxane additive was found not to improve toughness at all for the DGEBA‐based resin system due to the poor dispersion within the epoxy matrix. The TGDDM‐based resin systems were found not to be toughened by any of the additives due to the lack of plastic deformation of the highly cross‐linked epoxy network Copyright © 2003 Society of Chemical Industry     

Thermal degradation and flammability of P/Si polysilsesquioxane epoxy nanocomposites

A thermal stable epoxy nanocomposite prepared from the 4,4′‐diglycidylether bisphenol A (DGEBA) and the P/Si ladder‐like polysilsesquioxane (PSSQ). The activation energies of thermal degradation were calculated by Kissinger's and Ozawa's methods. The higher ladder‐like PSSQ content not only increase the oligomer content but also generate the steric hindrance. Which steric hindrance influence the epoxy/amine curing reaction of the modified epoxy system was more than the pristine DGEBA epoxy system. The P‐Si synergistic effect on the thermal stability of the nanocomposites was discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A study on formation and stability of epoxy resin inverse concentrated water/oil emulsion

Inverse concentrated emulsions were prepared using aqueous colloidal silica suspension as the hydrophilic dispersed phase and a solution of diglycidyl ether of bisphenol‐A (DGEBA), its curing agent polyamide resin, low molecular weight 650, surfactant nonyl phenol polyoxyethylene ether (NPE‐4) in 4‐methyl‐2‐pentanon as the continuous phase, which was expected to be used as the precursors of preparation of porous epoxy resins. The stability, i.e., the resistance to phase separation was studied. The effects of various parameters on the stability of the concentrated emulsions were investigated. The colloidal silica can strengthen the steric repulsion in the system and improve the stability. Viscosity of both phases played a major role in the stability. Precuring of the continuous phase provided an increased initial viscosity and enhanced the stability. Lower volume fraction of the dispersed phase can help to maintain stability of the concentrated emulsions. Properly increasing the curing rate, the concentrated emulsions may acquire a high viscosity in a short time, which retarded the phase separation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel imidazole derivatives with recoverable activity as latent curing agents for epoxy

A series of latent curing agents were developed by replacing the hydrogen atom on secondary amine in imidazole with methoxy polyethylene glycol maleate diesters via Michael addition reaction. Methoxy polyethylene glycol maleate diesters with different molecular weight also restrained the reactivity of tertiary amine in imidazole ring. The curing properties and pot-life of the modified imidazole/epoxy systems were measured by differential scanning calorimeter and rotational rheometer. The modified imidazole/epoxy system could be cured quickly at 175°C. The modified imidazole shows good latency. After stored for more than 1 month, viscosity of modified imidazole/epoxy system remains unchanged. The longer chain polyether had the better thermal latency these curing agents had. Compared with unmodified imidazole, the novel latent curing agents led to better impact strength for cured epoxy. However, the compatibility between epoxy and latent curing agent will get worse if the molecular weight of polyether unite is over 750.