Cure Kinetics of Poly(acrylonitrile-butadiene-styrene) Modified Epoxy–Amine System

The cure kinetics of epoxy based on the diglycidyl ether of bisphenol A (DGEBA) modified with different amounts of poly(acrylonitrile-butadiene-styrene) (ABS) and cured with 4,4′-diaminodiphenylsulfone (DDS) was investigated by employing differential scanning calorimetry (DSC). The curing reaction was followed by using an isothermal approach over the temperature range 150–180°C. The amount of ABS in the blends was 3.6, 6.9, 10 and 12.9 wt%. Blending of ABS in the epoxy monomer did not change the reaction mechanism of the epoxy network formation, but the reaction rate seems to be decreased with the addition of the thermoplastic. A phenomenological kinetic model was used for kinetic analysis. Activation energies and kinetic parameters were determined by fitting the kinetic model with experimental data. Diffusion control was incorporated to describe the cure in the latter stages, predicting the cure kinetics over the whole range of conversion. The reaction rates for the epoxy blends were found to be lower than that of the neat epoxy. The reaction rates decreased when the ABS contents was increased, due to the dilution effect caused by the ABS on the epoxy/amine reaction mixture.     

Kinetic studies of the polymerization of an epoxy resin modified with rhodamine B

Novel fluorescent materials were satisfactorily synthesized. With this aim, an epoxy resin based on diglycidyl ether of bisphenol A (DGEBA) was reacted with a laser dye, rhodamine B (RB), to achieve an epoxy-based prepolymer. Then, a diamine, m-xylylenediamine (MXDA), was used as hardener with the purpose of obtaining a crosslinked polymer. The curing conditions strongly influence the intended final properties and the optimization of the curing requires a reliable kinetic model. For that reason, this work presents the kinetic study of the polymerization of the epoxy resin by differential scanning calorimetry (DSC) in isothermal mode as well as by Fourier transform infrared spectroscopy (FTIR). DSC data were fitted using a Kamal autocatalytic equation. Conversion as a function of reaction time curves obtained by means of both techniques agreed well. In addition, the synthesized epoxy-based materials were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR) and their fluorescent properties were also analysed.     

Epoxy resins. II. The preparation,characterization, and curing of epoxy resins and their copolymers

A polymer with high aromatic ring content in the chain backbone usually has high heat and flame resistance. Three diglycidyl ethers of epoxy resins were prepared from bisphenol A (DGEBA), phenolphthalein (DGEPP), and 9,9-bis(4-hydroxyphenyl)fluorene (DGEBF) in a study of the relation between the cured polymer structure and properties. The epoxy resin prepared from phenolphthalein was separated by liquid chromatography and three fractions were obtained. The fractions had a basic structure of 3,3-disubstituted phthalide and differed only in molecular weight. The DGEPP resin changed color from yellow to red after mixing with trimethoxyboroxine (TMB), the curing agent, and to orange after completing the curing cycle. To prepare a highly crosslinked material with good thermal stability, TMB with three active Lewis sites in a molecule was used as the curing agent. The reactivity of the three different resins toward TMB, measured by differential scanning calorimetry (DSC), was DGEBA > DGEBF > DGEPP. For the same curing conditions the order of crosslink density was DGEBA > DGEPP > DGEBF. To modify the flammability of DGEBA, the conventional epoxy resin, it was copolymerized with DGEPP and DGEBF, the higher-performance epoxy resins. The glass transition temperatures of poly(DGEBA-co-DGEPP) and poly(DGEBA-co-DGEBF) systems deviated from this relationship. The DGEBF copolymers showed an increased char residue (40 wt % at 700°C) at 20 mole % of DGEBF. This deviation may be due to the lower crosslinking density of this system.     

Morphologic and kinetic study of an epoxy-poly(ethyleneoxide) system. The fluorescence to predict miscibility

The kinetic of the curing process in the ethylenediamine (EDA)-poly (bisphenol A-co-epichlorohydrin) glycidyl end-capped (DGEBA) mixture modified with poly(ethylene oxide) (PEO) was studied. The epoxy component was labeled with a fluorescence group (dansyl) treating the DGEBA with the reactive dansyl derivative DNS-EDA. Dynamic DSC experiments were carried out and from their results the effect of the PEO composition on the epoxy curing was discussed. Furthermore, the effect of cure temperature and PEO composition on the morphology and crystallinity of the blend were studied as well. The morphologic study was carried out using complementarily optical transmission (TOM) and epifluorescence (EFM) microscopy. It was observed that: i) the addition of a non-reactive thermoplastic leads to a dilution effect of the reactive groups and therefore a decrease of the epoxy amine reaction rate; ii) the PEO composition does not seem to affect the non catalyzed process of the epoxy curing, while an increase in the PEO fraction within the epoxy/PEO mixture seems to change the mechanism of the cure reaction; iii) dynamic DSC scans, TOM and EFM images and steady state fluorescence spectra of the cured samples suggest that when the curing temperature increases there is an increase in the miscibility between PEO and the epoxy-amine reaction mixture; and iv) a reduction in the PEO/cured epoxy miscibility as the fraction of PEO increases was observed.     

Curing kinetics of bio-based epoxy resin-toughened DGEBA epoxy resin blend

In the present study, TEIA bioresin was blended with the diglycidyl ether bisphenol A (DGEBA) epoxy resin in different ratios (i.e. 10, 20, 30, 40 mass%), cured with methylhexahydrophthalic anhydride curing agent in the presence of 2-methylimidazole catalyst. The optimized composition of DGEBA and TEIA bioresin blends system was employed as an adhesive strength. The adhesive strength of the TEIA-modified DGEBA epoxy resin blend system was increased from 4.14 to 6.31 MPa on an aluminium substrate compared to the DGEBA epoxy resin. The curing kinetics of non-isothermal, DGEBA epoxy resin and its bio-based blend systems were investigated employing differential scanning calorimetry. An increase in the peak temperature and reduction in a heat of curing as well as activation energy in DGEBA epoxy resin were observed with the addition of TEIA bioresin content. The activation energy (E_a) of the DGEBA resin and their bio-based blend system were obtained from Kissinger and Flynn–Wall–Ozawa methods.

     

The curing kinetics and mechanical properties of epoxy resin composites reinforced by PEEK microparticles

In this paper, a polyether-ether-ketone (PEEK)/epoxy composite was prepared by using PEEK microparticles as the reinforcement. The nonisothermal differential scanning calorimetry (DSC) test was used to evaluate the curing reaction of PEEK/epoxy resin system. The curing kinetics of this system were examined utilizing nonisothermal kinetic analyses (Kissinger and Ozawa), isoconversional methods (Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) and an autocatalytic reaction model. During these analyses, the kinetic parameters and models were obtained, the curing behavior of PEEK/epoxy resin system under dynamic conditions was predicted. The results show that isoconversional methods can adequately interpret the curing behavior of PEEK/epoxy resin system and that the theoretical DSC curves calculated by the autocatalytic reaction model are in good agreement with experimental data. Furthermore, the tensile elongation at break, tensile strength, flexural strength, compression strength and compression modulus increased by 81.6%, 33.66%, 36.53%, 10.98% and 15.14%, respectively, when PEEK microparticles were added in epoxy resin composites.     

Organic/inorganic hybrid composites from cubic silsesquioxanes.

A new class of epoxy nanocomposites with completely defined organic/inorganic phases was prepared by reacting octakis(glycidyldimethylsiloxy)octasilsesquioxane [(glydicylMe(2)SiOSiO(1.5))(8)] (OG) with diaminodiphenylmethane (DDM) at various compositional ratios. The effects of reaction curing conditions on nanostructural organization and mechanical properties were explored. A commercial epoxy resin based on the diglycidyl ether of bisphenol A (DGEBA) was used as a reference material throughout these studies. FTIR was used to follow the curing process and to demonstrate that the silsesquioxane structure is preserved during processing. OG/DDM composites possess comparable tensile moduli (E) and fracture toughness (K(IC)) to, and better thermal stabilities than, DGEBA/DDM cured under similar conditions. Dynamic mechanical analysis and model reaction studies suggest that the maximum cross-link density is obtained at N = 0.5 (NH(2):epoxy groups = 0.5) whereas the mechanical properties are maximized at N = 1.0. Digestion of the inorganic core with HF followed by GPC analysis of the resulting organic tether fragments when combined with the model reaction studies confirms that, at N = 0.5, each organic tether connects four cubes, while, at N = 1.0, linear tethers connecting two cubes dominate the network structure. Thus, well-defined nanocomposites with controlled variation of the organic tether architecture can be made and their properties assessed.     

Isothermal cure kinetics of epoxy/phenol‐novolac resin blend system initiated by cationic latent thermal catalyst

The investigation of the cure kinetics of a diglycidyl ether of bisphenol A (DGEBA)/phenol‐novolac blend system with different phenolic contents initiated by a cationic latent thermal catalyst [N‐benzylpyrazinium hexafluoroantimonate (BPH)] was performed by means of the analysis of isothermal experiments using a differential scanning calorimetry (DSC). Latent properties were investigated by measuring the conversion as a function of curing temperature using a dynamic DSC method. The results indicated that the BPH in this system for cure is a significant thermal latent initiator and has good latent thermal properties. The cure reaction of the blend system using BPH as a curing agent was strongly dependent on the cure temperature and proceeded through an autocatalytic kinetic mechanism that was accelerated by the hydroxyl group produced through the reaction between DGEBA and BPH. At a specific conversion region, once vitrification took place, the cure reaction of the epoxy/phenol‐novolac/BPH blend system was controlled by a diffusion‐control cure reaction rather than by an autocatalytic reaction. The kinetic constants k₁ and k₂ and the cure activation energies E₁ and E₂ obtained by the Arrhenius temperature dependence equation of the epoxy/phenol‐novolac/BPH blend system were mainly discussed as increasing the content of the phenol‐novolac resin to the epoxy neat resin. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2945–2956, 2000     

Epoxy resin/poly(ϵ‐caprolactone) blends cured with 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane. I. Miscibility and crystallization kinetics

Crystalline thermosetting blends composed of 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane (BAPP)‐cured epoxy resin (ER) and poly(?‐caprolactone) (PCL) were prepared via the in situ curing reaction of epoxy monomers in the presence of PCL, which started from initially homogeneous mixtures of diglycidyl ether of bisphenol A (DGEBA), BAPP, and PCL. The miscibility of the blends after and before the curing reaction was established with differential scanning calorimetry and dynamic mechanical analysis. Single and composition‐dependent glass‐transition temperatures (T_g's) were observed in the entire blend composition after and before the crosslinking reaction. The experimental T_g's were in good agreement with the prediction by the Fox and Gordon–Taylor equations. The curing reaction caused a considerable increase in the overall crystallization rate and dramatically influenced the mechanism of nucleation and the growth of the PCL crystals. The equilibrium melting point depression was observed for the blends. An analysis of the kinetic data according to the Hoffman–Lauritzen crystallization kinetic theory showed that with an increasing amorphous content, the surface energy of the extremity surfaces increased dramatically for DGEBA/PCL blends but decreased for ER/PCL blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1085–1098, 2003     

非等温法研究TGDDM/DDS体系固化反应动力学

采用DSC对4,4′-四缩水甘油基二氨基二苯基甲烷(TGDDM)和3,3′-二氨基二苯基砜(DDS)体系的固化反应动力学进行了研究.分别通过n级反应法和Malek的最大概然机理函数法确定了固化反应机理函数,求解了固化反应动力学参数,得到了固化反应动力学模型.结果表明,通过Kissinger,Crane方法求解动力学参数所得到的n级反应模型与实验值差别较大;而采用Malek方法判别机理,表明该固化反应按照自催化反应机理进行,实验得到的DSC曲线与模型计算所得到的曲线吻合的较好,所确立的模型在5~20K/min的升温速率下能较好地描述TGDDM/DDS体系的固化反应过程,并为工艺参数的选择和工艺窗口的优化提供了理论依据.     

Curing and thermomechanical properties of off-stoichiometric anhydride–epoxy thermosets

In the present work, we report the preparation and characterization of a new family of thermosets based on off-stoichiometric anhydride–epoxy formulations in the presence of an anionic initiator. Diglycidyl ether of bisphenol A (DGEBA) and hexahydro-4-methylphthalic anhydride (HHMPA) have been used as epoxy and anhydride comonomers, respectively, and 1-methylimidazole (1MI) has been used as anionic initiator. The isothermal curing kinetics and the thermal properties of the stoichiometric and the off-stoichiometric systems have been compared. The kinetics of the isothermal curing has been analyzed by differential scanning calorimetry (DSC) using an isoconversional method and the ?esták–Berggren equation to determine the activation energy, the frequency factor and the reaction orders. The materials obtained were characterized by DSC and dynamic mechanical analysis. Gelation during epoxy–anhydride condensation was determined by thermomechanical analysis. At the same curing temperature, the reaction is faster in the system with excess of epoxy groups. However, the glass transition temperatures of the partially cured stoichiometric system are greater. The gelation time of the off-stoichiometric system is shorter than that of the stoichiometric one. The results indicate that the dual-curing character of off-stoichiometric DGEBA/HHMPA thermosets with 1MI as anionic initiator makes them suitable for multistage curing processes with easy control of degree of cure and material properties in the intermediate stage and enhanced final material properties.

     

Study of cure kinetics of epoxy-silica organic-inorganic hybrid materials

Cure kinetics of organic-inorganic hybrids based on epoxy resin was investigated, using differential scanning calorimetry (DSC). Thermoset hybrid materials were prepared from diglycidyl ether of bisphenol A (DGEBA) as organic precursor, and 3-glycidyloxypropyltrimethoxysilane (GLYMO) as inorganic precursor. Precursors were polymerised simultaneously using poly(oxypropylene)diamine (Jeffamine D230) as a curing agent. Isothermal DSC characterisation of DGEBA/Jeffamine system and two hybrid DGEBA/GLYMO/Jeffamine systems, with DGEBA and GLYMO mixed in mass ratios of 2:1 and 1:1, respectively, was performed at different temperatures. Applicability of empirical models, commonly used to describe the curing kinetics of thermosets, to hybrid systems was investigated, and the resulting parameters were tested on dynamic DSC scans. Additionally, prepared materials were studied by FTIR and the extraction in tetrahydrofuran. The presence of inorganic phase was found to hinder complete cross-linking of organic phase and influence the kinetics of cure.     

Acceleration mechanisms in curing reactions involving model systems

The mechanisms involving some of the most common accelerators in the curing reactions of epoxy resins have been investigated by use of model systems. Phenyl glycidyl ether was used as a model compound. The characterization of the reaction products was mainly carried out by High-Performance-Liquid-Chromatography and by preparative methods. Special attention was paid to the oligomerization reactions of the oxirane ring in the presence of tertiary amines. Three different types of oligomers depending on phenyl glycidyl ethers are discussed. The mechanisms of multifunctional accelerators such as imidazoles or phenol-MANNICH-base-compounds are much more difficult. The extraordinary interaction of imidazoles depends on the formation of different oligomers. Furthermore, the cleavage of the imidazole ring was observed. It is possible that the glycidyl ether oligomerization plays an important role in understanding the network structure. Some aspects of the accelerating effect of tertiary amines in the curing of glycidyl ethers with acid anhydrides were likewise discussed. The results obtained using these model reactions may be applied to influence the curing process in commercial epoxy resin systems.     

Phosphorus-containing thermosets obtained by cationic copolymerisation of glycidyl compounds with a spiroorthoester or γ-butyrolactone

The synthesis of a bis[(1,4,6-trioxaspiro[4.4]nonan-2-yl)-methyloxy] ethane (bisSOE) and its copolymerisation with mixtures of diglycidyl ether of bisphenol A (DGEBA) and different phosphorus-containing glycidyl compounds led to materials with enhanced flame retardancy and low shrinkage on crosslinking. Analogous materials were obtained by reaction of mixtures where the spiroorthoester (SOE) is formed in the reaction medium from γ-butyrolactone and a diglycidyl compound.The incorporation of phosphorus in the networks increases the LOI values and all crosslinked polymers showed a slight shrinkage after curing, much lower than that observed in conventional epoxy resins. The materials from preformed SOE showed lower shrinkage than the analogues from lactone and epoxy groups.     

Rheokinetic cure characterization of epoxy–anhydride polymer system with shape memory characteristics

An epoxy resin capable of exhibiting shape memory property was derived by curing diglycidyl ether of bisphenol A (DGEBA) with a blend of carboxy telechelic poly(tetramethyleneoxide) (PTAC) and pyromellitic dianhydride (PMDA). The cure kinetics of DGEBA/PTAC/PMDA blend of varying compositions was investigated using isothermal rheological analysis. The overall reaction conformed to a second-order autocatalytic model. The kinetic parameters including reaction order, kinetic constants and activation energy were determined. The results showed that increase of PTAC decreased the overall activation energy and frequency factor of the cure reaction. This effect resulted in a diminution of the overall rate of curing. The catalysis by PTAC has its origin from the activation of epoxy groups by the protons of the COOH groups. The autocatalysis was caused by the COOH groups generated by the reaction of alcohol groups with anhydride. The activation energy for the autocatalysis was more than that for the primary reaction as the COOH groups responsible for autocatalysis were generated on a sterically hindered polymer backbone. The kinetics helped generate a master equation conforming to second-order autocatalytic model that could predict the cure profile of a specified resin system at a given temperature, leading to cure optimization.     

Effects of liquid crystalline structure formation on the curing kinetics of an epoxy resin

The curing kinetics of a system containing 4,4′-diglycidyloxy-α-methylstilbene (DOMS) and different functionality amines, N-ethylaniline (NEA), aniline, benzenesulfonamide (BSA), and sulfanilamide (SAA), have been studied by differential scanning calorimetry (DSC) under isothermal conditions. The phase transformations during curing of the systems have been monitored by a crosspolarized optical microscope equipped with a hot-stage and photo detector. It has been found that the growth of a nematic liquid crystal structure does not cause a discrepancy from the autocatalytic model for the reactions between aniline and epoxy. There is no liquid crystalline structure formed for the systems containing NEA or BSA, which follow the autocatalytic kinetic models within the temperature range of 120–150°C. For the curing reactions between DOMS and SAA, there is a big deviation from the autocatalytic model when the liquid crystals transfer from a nematic structure to a smectic structure. Unlike the usual decrease of reaction rate resulting from diffusion in a heterogeneous reaction, the reaction rate is enhanced. A modified kinetic model has been constructed for this reaction system by introducing a pseudoconcentration term caused from the liquid crystalline structure formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1105–1124, 1997     

2-乙基-4-甲基咪唑固化环氧树脂体系动力学模型

由2-乙基-4-甲基咪唑(2,4-EMI)固化双酚A二缩水甘油醚型环氧树脂(DGEBA)的等温差示扫描量热(DSC)实验结果发现固化反应分两阶段进行,催化聚合反应有一诱导期.由DSC测试结果求得催化聚合反应的速率常数.从反应机理出发,以诱导期为边界,建立两阶段的微观固化动力学模型.从扩散的角度在模型中引入临界固化度(αc)和扩散因子,进一步建立扩散控制固化动力学模型,对不同2,4-EMI含量和固化温度(Tc)的体系,计算得到αc.研究发现扩散因素对固化动力学影响较大,固化反应前期由化学动力学控制,后期由扩散因素控制;αc主要由体系的玻璃化转变决定,Tc越高,体系玻璃化转变时对应的固化度越大,cα越大.     

Optically clear simulataneous interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and epoxy. II. Kinetic study

Simultaneous interpenetrating polymer networks (SINs) based on diglycidyl ether of bis-phenol A (DGEBA) and poly(ethylene glycol) diacrylate (PEGDA) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using benzoyl peroxide (BPO) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 45, 55, 63, and 70°C. Concentration changes for both the epoxide and C?C bond were monitored with FTIR. A rate expression for DGEBA cure kinetics was established with a model reaction of phenyl glycidyl ether (PGE) and benzylamine. Experimental results revealed that lower rate constants and higher activation energy for the SIN were found, compared with those for the constituent DGEBA and PEGDA network formation. A model of network interlock was proposed to account for this phenomenon. During simultaneous cure of DGEBA and PEGDA, the interlock (mutual entanglement) between DGEBA and PEGDA networks provided a sterically hindered environment, which subsequently increased the activation energy and reduced cure rates for both DGEBA and PEGDA. © 1993 John Wiley & Sons, Inc.     

Carbonyldiimidazole‐accelerated efficient cure of epoxidized soybean oil with dicyandiamide

This study investigates the curing of epoxidized soybean oil (ESO) using dicyandiamide (DICY) and combinations of DICY with several accelerators as curing agents. The differential scanning calorimetry (DSC) results indicated that carbonyldiimidazole (CDI) is a highly efficient accelerator for the ESO‐DICY curing system. CDI accelerated ESO‐DICY curing system can gel within a short period of 13 min at 190 °C. The activation energies of the ESO‐DICY curing systems with and without CDI are 95 and 121 kJ mol^?1, respectively. Similar acceleration effect was observed in the ESO‐diglycidyl ether of biphenyl A (DGEBA) blending formulations. When the molar part of the glycidyl epoxy groups of DGEBA was equal to the internal epoxy groups of ESO in the mixture, gelation of the DICY curing system accelerated by CDI was achieved in 3 min at 160 °C. Furthermore, the DSC results with FTIR analysis suggest that the stoichiometric curing molar ratio was 3 ESO epoxy units per 1 DICY molecule. Two epoxy units reacted with DICY to give secondary alcohols, while the other one linked to the nitrile group. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 375–382     

Advanced flame‐retardant epoxy resins from phosphorus‐containing diol

Phosphorus‐containing epoxy systems were prepared from isobutylbis(hydroxypropyl)phosphine oxide (IHPO) and diglycidyl ether of bisphenol A (DGEBA). Diethyl‐N,N‐bis(2‐hydroxyethyl) aminomethyl phosphonate (Fyrol 6) could not be incorporated into the epoxy backbone by a reaction with either epichlorohydrin or DGEBA because intramolecular cyclization took place. The curing behavior of the IHPO–DGEBA prepolymer with two primary amines was studied, and materials with moderate glass‐transition temperatures were obtained. V‐0 materials were obtained when the resins were tested for ignition resistance with the UL‐94 test. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3510–3515, 2005