Kinetic study on epoxy bisphenol‐A diacrylate IPN formation

Interpenetrating polymer networks (IPN) based on diglycidyl ether of bisphenol‐A (DGEBA) and bishenol‐A diacrylate (BADA) in weight ratios of 100/0, 50/50, and 0/100 were blended and were cured simultaneously by using benzoyl peroxide (BPO) and 4,4′‐methylenedianiline (MDA) as curing agents. Kinetic study during IPN formation was carried out at 65, 70, 75 and 80 °C. Absorbance changes at 1623.3 cm⁻¹ and 914 cm⁻¹ relating to concentration changes of CC and epoxide were monitored with Fourier‐transform infrared spectroscopy (FTIR). The epoxide cure kinetic data revealed a combination of non‐catalytic bimolecular reaction and a catalyzed termolecular reaction, while the CC cure kinetic data fitted a first‐order reaction. The calculated kinetic parameters indicated decreased rate constants and increased activation energies of the IPN compared with those of the individual components. Presumably, chain entanglements between the two networks provide a sterically hindered environment for the cure reactions and vitrification restrains the chain mobility, accounting for the kinetic parameters. © 1999 Society of Chemical Industry     

Semi-IPNs formed from poly(ethylene glycol monomethyl ether acrylate) and an epoxy thermoset

Poly(ethylene glycol monomethyl ether acrylate) (PEGMEA) was synthesized from the reaction of poly(ethylene glycol monomethyl ether) (PEGME) with acryloyl chloride. Semi-IPNs based on various weight ratios of diglycidyl ether of bisphenol A (DGEBA)/PEGMEA were prepared, using isophronediamine (IPDA) and 2,2′-azo-bis(isobutyronitrile) (AIBN) as curing agents. The glass transition temperature and exothermic peak shifts were studied with differential scanning calorimetry (DSC). Viscosity changes during semi-IPN formation were measured with a Brookfield viscometer. Dynamic mechanical properties were investigated by rheometric dynamic spectroscopy (RDS). Stress–strain curves were obtained with an Instron tensile tester, while impact resistance was measured with a computer aided falling dart impact tester. Experimental results revealed retarded curing rates for all semi-IPNs, as evidenced from the shifts of curing exothermic peaks to higher temperatures, together with retarded viscosity increases during semi-IPN formation. These phenomena were interpreted in terms of chain entanglement between epoxy and PEGMEA. Nevertheless, the semi-IPNs indicated good compatibility as inferred from a single T_g in DSC and a single damping peak in RDS for each semi-IPN. Improved tensile stress and strain along with toughness improvements were noticed for this semi-IPN system. Shear band yielding was proposed to interpret this result. © 1999 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     

Chemorheology on simultaneous IPN formation of epoxy resin and unsaturated polyester

Study of the simultaneous interpenetrating polymer network (IPN) between diglycidyl ether of bisphenol-A (DGEBA) and unsaturated polyester (UP) was carried out at ambient temperature. Fourier transform infrared (FTIR) spectroscopy was employed to investigate the intermolecular H-bonding and functional group changes. Viscosity changes due to H-bonding and crosslinking were examined with a Brookfield viscometer. Gelation time was measured by a Techne gelation timer. Complexation between Co(II) (the promoter for UP cure) and diamine (the curing agent for DGEBA) was detected with UV-visible spectrometer. Experimental evidence revealed that intermolecular interactions were observed in systems such as DGEBA/UP, DGEBA/diamine, Co(II)/diamine, DGEBA/uncured UP, and UP/uncured DGEBA. All such interactions had measurable effects on the curing behaviors for both networks, as were indicated by the viscosity changes and gelation time. The IPNs thus obtained were further characterized with rheometric dynamic spectroscopy (RDS) and differential scanning calorimetry (DSC). Partial compatibility between UP and DGEBA networks was evidenced from a main damping peak with a shoulder near glass transition temperature (T_g) for lower UP content; while at higher UP content, only a main damping peak near T_g was observed. DSC revealed a broad glass transition for all IPNs. The resultant IPN materials were all transparent. © 1992 John Wiley & Sons, Inc.     

Toughened interpenetrating polymer network materials based on unsaturated polyester and epoxy

Simultaneous interpenetrating polymer networks (IPNs) based on epoxy (diglycidyl ether of bisphenol A) and unsaturated polyester (UP) were prepared by using m‐xylenediamine and benzoyl peroxide as curing agents. A single glass transition temperature for each IPN was observed with differential scanning calorimetry, which suggests good compatibility of epoxy and UP. This compatibility was further confirmed by the single damping peak of the rheometric dynamic spectroscopy. Curing behaviors were studied with dynamic differential scanning calorimetry, and the curing rates were measured with a Brookfield RTV viscometer. It was noted that an interlock between the two growing networks did exist and led to a retarded viscosity increase. However, the hydroxyl end groups in UP catalyzed the curing reaction of epoxy; in some IPNs where the hydroxyl concentration was high enough, such catalytic effect predominated the network interlock effect, leading to fast viscosity increases. In addition, the entanglement of the two interlocked networks played an important role in cracking energy absorption and reflected in a toughness improvement. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 585–592, 1999     

Kinetic analysis of curing behavior of diglycidyl ether of bisphenol A with imidazoles using differential scanning calorimetry techniques

The curing kinetics and mechanisms of diglycidyl ether of bisphenol A (DGEBA) using imidazole (H‐NI) and 1‐methyl imidazole (1‐MI) as curing agents are studied with differential scanning calorimetry (DSC) under isothermal (90–120°C) and dynamic conditions (50–250°C). The isothermal DSC thermograms of curing DGEBA with H‐NI and 1‐MI curing agents show two exothermic peaks. These peaks are assigned to the processes of adduct formation and etherification. These results indicate that there is no difference in the initiation mechanism of 1‐unsubstituted (H‐NI) and 1‐substituted (1‐MI) imidazoles in the curing reaction with epoxy resin. A kinetic analysis is performed using different kinetic models. The activation energies obtained from DSC scanning runs using the Ozawa and Kissinger methods are similar and in the range of 75–79 and 76–82 kJ/mol for DGEBA/H‐NI and DGEBA/1‐MI systems, respectively. These values compare well with the activation energies obtained from isothermal DSC experiments using the autocatalytic method (74–77 kJ/mol). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2634–2641, 2006     

Conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid

We developed a conductive epoxy/amine system containing polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA). The curing behaviors of diglycidyl ether of bisphenol A with triethylenetetramine (TETA), PAni.DBSA, and both amine compounds at different concentrations were investigated by differential scanning calorimetry (DSC). Epoxy/TETA systems containing PAni.DBSA presented two distinct exothermic peaks at 90°C due to the cure by TETA as a hardener and at 236°C related to PAni.DBSA as the curing agent. The presence of PAni.DBSA in the systems constituted by epoxy/hardener in stoichiometric proportions resulted in a decrease in the glass‐transition temperature of the epoxy matrix, as indicated by DSC and dielectric analyses. Electrical conductivity was determined in the epoxy/amine networks, with the TETA concentration kept constant and also in stoichiometric proportions of mixed hardener (TETA + PAni.DBSA) to epoxy resin. The last condition resulted in a higher electrical conductivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4059–4065, 2006     

Synthesis,characterization, and thermomechanical properties of liquid crystalline epoxy resin containing ketone mesogen

This study focuses on the synthesis of a novel liquid crystalline epoxy resin (LCER) based on ketone mesogenic group. The chemical structure, melting range, and liquid‐crystalline phase transition behavior of the LCER were characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). Two endothermal peaks and one exothermal peak appeared in the DSC curves. A birefringent liquid crystalline texture was observed with POM during heating. The curing reaction of the LCER was monitored by DSC using diaminodipheylmethane (DDM) and diaminodiphenylsulfone (DDS) as curing agents, respectively. The results showed that the curing reaction of LCER/DDM proceeded faster than that of LCER/DDS in the initial stage. Birefringence was observed with POM during the curing processes. The results of thermomechanical properties showed that the glass transition temperatures of the cured LCERs were higher than 230°C, and that the LCER crosslinked networks were thermally stable up to 360°C. The LCER crosslinked networks showed much higher glass transition temperature, storage modulus, and thermal conductivity, and a lower coefficient of thermal expansion both in the glassy region and the rubbery region compared to those of a common epoxy resin (diglycidyl ether of bisphenol A). POLYM. ENG. SCI., 57:424–431, 2017. © 2016 Society of Plastics Engineers     

Thermo-oxidative aging of epoxy coating systems

The thermo-oxidative behavior of unformulated (unfilled) samples of epoxy coatings has been studied at five temperatures ranging from 70 °C to 150 °C. Two epoxy networks based on diglycidyl ether of bisphenol A (DGEBA), respectively, cured by jeffamine (POPA) or polyamidoamine (PAA) were compared. Infrared spectrophotometry (IR), differential scanning (DSC) and sol–gel analysis (SGA) were used to monitor structural changes.     

Effect of the epoxy molecular weight on the properties of a cyanate ester/epoxy resin system

Bisphenol A dicyanate (BADCy) was modified by diglycidyl ether of bisphenol A epoxy resins with different molecular weights [E20 (weight‐average molecular weight = 1000) and E51 (weight‐average molecular weight = 400)] to investigate the effects of the epoxy molecular weight on the properties of the modified systems. The reactions were monitored with differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy, and the results showed that more pentacyclic oxazolidinone rings were formed in BADCy/E51 than in BADCy/E20 with the same epoxy resin weight content. DSC showed that BADCy/E20 had a lower curing temperature than BADCy/E51 because of the higher concentration of hydroxyl groups (? OH) in E20. Thermal, moisture absorption, and mechanical testing showed that E51‐modified BADCy performed better because of its lower molecular weight. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1744–1750, 2006     

Dynamic light scattering and ultrasonic investigations during the cure reaction of an epoxy resin

Brillouin scattering (BS), photon correlation spectroscopy (PCS), and ultrasonic (US) measurements were conducted to study the curing process of diglycidyl ether of bisphenol A with butane-1,4-diol at a curing temperature of 100°C. The experimental techniques probe the primary glass-rubber transition during the curing reaction. The primary relaxation time τ obtained from the BS and US velocity and absorption increases with curing time and hence the BS experiment measures τ at earlier stages of cure than the US experiment. The relaxation times at a different extent of reaction and for different measuring temperatures are consistent with BS, US, PCS, and DSC measurements and conform to a single reduced Vogel–Fulcher–Hesse–Tamann equation. Furthermore, the US experiments show evidence of secondary relaxations in the epoxy system.     

Thermal and mechanical properties of aminopropoxylate-cured epoxy matrices

Bisphenol A diglycidyl ether–aminopropoxylate mixtures have been characterized with respect to their viscosities in the presence and absence of butanediol diglycidyl ether (reactive diluent), and their curing patterns have been studied at room temperature with or without 2,4,6-tris(dimethylaminomethyl)phenol (initiator/accelerator). A priori, these mixtures are expected to provide low connectivities to infinite networks at gelation, a prediction supported by the multiple glass-transition-temperature (T_g) behaviour of their cured forms. The effect of the aminopropoxylate curing agent chemistry/functionality, and the presence or absence of accelerator and reactive diluent on the tensile and impact behaviour of cured materials, is reported. An expectation of increased importance of polymerization with increases in the initiator/accelerator levels, alongside epoxy–amine addition reactions, has not been evidenced by the mechanical measurements. For diglycidyl ether bisphenol A–aminopropoxylate epoxy systems, in the glycidyl ether/reactive hydrogen molar ratio range 0·80 (set A) to 1·95 (set B), the tensile failure mode is brittle fracture. For the set A formulations, this mode of failure persists up to reactive diluent loadings of 1·01wt% based on the weight of bisphenol A diglycidyl ether. Beyond 1·01wt% reactive diluent loadings, the set A formulations show ductile failure with yielding; the tensile toughness increases with increases in reactive diluent levels. For the set B formulations, and for all reported loading levels of reactive diluent, the castings failed in brittle fashion with pronounced cavitation and stress whitening. © 1998 Society of Chemical Industry     

Degradable epoxy resins based on bisphenol A diglycidyl ether and silyl ether amine curing agents

A series of silyl ether amine curing agents were synthesized by selective substitution reactions of chloroalkylsilanes or the transetherification of alkoxysilanes. Crosslinked networks were prepared by mixing a stoichiometric ratio of bisphenol A diglycidyl ether (D.E.R 331) with the amine curing agents. The networks were characterized by ATR‐FTIR spectroscopy, TGA, DSC, and DMA. The onset of thermal degradation, glass transition temperatures, and storage moduli for the networks were 350 °C, 70–108 °C, and 5–25 MPa, respectively. The degradation behavior of the cured samples was monitored for 30 days in PBS, NaOH 5% (w/v), and HCl 5% (v/v) solutions and the degradation products were characterized by spectroscopic methods. The thermal, mechanical, and degradation studies indicated that crosslink density, T_g, storage modulus, and the rate of degradation were affected by the functionality of the amine curing agents and the number of hydrolyzable silyl ether bonds present per mole of curing agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44620.     

Curing behavior and mechanical behavior of fully and semi-interpenetrating polymer networks based on polyurethane and acrylics

Polyurethane (PU) was made by reacting stoichiometric equivalent of trimethylol propane (TMP) and desmodur L. Fully interpenetrating polymer networks (fully IPN's) of various compositions based on PU and poly(ethylene glycol) diacrylate (PEGDA) were prepared by blending various ratios of PU/PEGDA, and cured by benzoyl peroxide (BPO). Semi-interpenetrating polymer networks based on PU and poly(ethylene glycol) monomethyl ether of acrylate (PEGMEA) were prepared in a similar way. Shift of exothermic peaks during IPN formation were examined with dynamic DSC. Viscosity increases were investigated with a Brookfield RVT type viscometer. Dynamic mechanical properties were probed via a rheometric dynamic spectroscopy (RDS).Expermintal results revealed a good compatibility of both IPN systems, as evidenced from the single damping peak of the RDS curves for each composition. Shifts of exothermic peaks to higher temperatures during the formation of fully IPN were observed, especially for the composition of PU/PEGDA = 50/50, which showed an exothermic peak at the highest temperature. Experimental results also revealed delayed viscosity increases and decreased gel fractions for all fully IPN's. On the contrary, the semi-IPN did not exhibibt similar phenomena. All these findings supported an effect of network interlock during fully IPN formation. The existence of a network not only provided a sterically hindered environment, but also restrained the chain mobility of the growing network, and vice versa, thus retarding the curing rates of both networks. Network interlock also broadened the width of the half damping peak, T_1/2, and subsequently led to improved mechanical properties such as the impact resistance and Young's modulus of fully IPN material.     

Synthesis and epoxy curing of Mannich bases derived from bisphenol A and poly(oxyalkylene)diamine

A family of Mannich bases were prepared from the reaction of 2,2‐bis‐(4‐hydroxyphenyl)propane (bisphenol A or BPA), formaldehyde, and poly(oxyalkylene)diamines at 1 : 1 : 1 or 1 : 2 : 2 molar ratio. By varying the molar ratio of bisphenol A to amine and the chemical structures of poly(oxyalkylene)diamines, a series of products with multiple functionalities of primary/secondary amines, phenols, and poly(oxyalkylene) were prepared. The curing profiles of these products toward the diglycidyl ether of bisphenol A (DGEBA) were examined by a differential scanning calorimeter (DSC). The physical properties of these cured materials were correlated with the chemical structures of the Mannich bases. Compared with the poly(oxyalkylene)diamines, the built‐in phenol moiety in Mannich bases accelerated the curing rate. Both amine and phenol functionalities could be reactive sites toward diglycidyl ethers in a step‐wise fashion under catalytic (triphenylphosphine) and different temperature conditions. Furthermore, the cured polymers demonstrated improved properties including tensile and flexural strength in comparison with those cured by the corresponding poly(oxyalkylene)diamines. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 615–623, 2000     

Preparation of a light color cardanol-based curing agent and epoxy resin composite: Cure-induced phase separation and its effect on properties

A light color cardanol-based epoxy curing agent (MBCBE) was synthesized from cardanol butyl ether, formaldehyde and diethylenetriamine. In comparison, a phenalkamine with a similar structure was also prepared. The chemical structures were confirmed by GC–MS and FTIR. The cure behaviors of diglycidyl ether of bisphenol A (DGEBA) with these two curing agents was studied by differential scanning calorimetry (DSC). The morphology, mechanical properties, thermal properties of the cured epoxies were also investigated. The DSC results indicated that MBCBE is less reactive than the phenalkamine. The morphology of the cured MBCBE/DGEBA consisted of cavities dispersed within a continuous epoxy matrix. The cavities markedly improved the lap shear strength and impact strength of the cured resin. Both the two cured resins indicated a two-stage decomposition mechanism. Compared with PKA/DGEBA, the weight loss of MBCBE/DGEBA at the first stage was mainly resulted from the dispersed phase in the epoxy matrix.     

Influence of the epoxy functionalization of multiwall carbon nanotubes on the nonisothermal cure kinetics and thermal properties of epoxy/multiwall carbon nanotube nanocomposites

Multiwall carbon nanotubes were functionalized with epoxy groups by chemical modification in four stages. At each stage, the compound was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). Epoxy composite samples were prepared by mixing diglycidyl ether of bisphenol A‐based epoxy resin and synthetic epoxy‐functionalized multiwall carbon nanotube (E‐MWCNT) with different percentages (1, 3, 6, 9, 12, and 15%) in acetone. Ultrasonic dispersion was used to produce homogenous blends. The optimum ratio of the reacting components (9%) was investigated by total enthalpy of the curing reaction from differential scanning calorimetry (DSC) thermograms. The kinetics of the curing reaction for epoxy composites with 4,4′‐diaminodiphenylsolfon as a curing agent was studied by means of a DSC nonisothermal technique. The kinetic parameters such as activation energy, pre‐exponential factor, and rate constant were obtained from DSC data. The structure ofthe nanocomposites and dispersion of the E‐MWCNTs in the nanocomposites were observed using SEM, and the thermal properties were studied by thermogravimetric analysis. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Investigations on the curing of epoxy resins with hexahydrophthalic anhydride

The bifunctional epoxides bisphenol A diglycidyl ether (BADGE) and hexahydrophthalic diglycidyl ester (HHDGE) as well as the monoepoxides phenyl glycidyl ether (PGE) and cyclohexane carboxylic acid glycidyl ester (CHGE) were cured with hexahydrophthalic anhydride (HHPA) in the presence of benzyldimethylamine (BDMA) or 1-methylimidazole (1-MI) as catalysts at 100–140°C. Investigations of the curing kinetics gave sigmoidal-shaped curves with marked induction periods. IR analysis of the cured products revealed that the propagation proceeds not only by the esterification reaction of epoxide with anhydride but also by chain anhydride formation by the reaction of carboxylate with anhydride groups. ¹³C-NMR investigations of the soluble polymers showed that most of the peaks resulting from double bonds could not be assigned to structures formed by initiation reactions that had previously been proposed for the anhydride curing of epoxides. In analogy to a postulated mechanism for the decarboxylation condensation of HHPA alone in the presence of tertiary amines, it is proposed that an isomerization product of HHPA is one of the molecules that initiate the curing reaction.     

TPP/PMMA复合物促进环氧树脂/酸酐体系的固化动力学研究

以三苯基膦(TPP)和甲基丙烯酸甲酯(MMA)为原料合成了TPP/PMMA复合物,用DSC研究了TPP/PMMA催化双酚A二缩水甘油醚(EP828)/甲基四氢苯酐(MTHPA)体系固化反应动力学。非等温固化动力学研究结果表明,转化率在20%～60%范围内,用Ozawa法能较好地描述环氧树脂/酸酐体系的固化反应过程。     

Modification of epoxy resin by isocyanate‐terminated polybutadiene

Hydroxy‐terminated polybutadiene was functionalized with isocyanate groups and employed in preparation of a block copolymer of polybutadiene and bisphenol A diglycidyl ether (DGEBA)‐based epoxy resin. The block copolymer was characterized by Fourier transform infrared (FTIR) spectroscopy and size‐exclusion chromatography (SEC). Cured blends of epoxy resin and hydroxy‐terminated polybutadiene (HTPB) or a corresponding block copolymer were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMTA), and scanning electron microscopy (SEM). All modified epoxy resin networks presented improved impact resistance with the addition of the rubber component at a proportion up to 10 wt % when compared to the neat cured resin. The modification with HTPB resulted in milky cured materials with phase‐separated morphology. Epoxy resin blends with the block copolymer resulted in cured transparent and flexible materials with outstanding impact resistance and lower glass transition temperatures. No phase separation was discernible in blends with the block copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 838–849, 2002