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

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

A dynamic mechanical study of the curing reaction of two epoxy resins

The curing behavior of two commercially formulated epoxy resins composed of the tetrafunctional amine dicyandiamide and with differing epoxy components, 4,4′-bisglycidylphenyl-2,2′-propane and the tetraglycidyl ether of methylene dianiline, is characterized by dynamic spring analysis. This supported viscoelastic technique is well suited to the determination of the onset of gelation under isothermal conditions but the method is not useful for monitoring later stages of reaction when the resins become more rigid. The activation energy for the curing of the two resins is about 87 kJ/mole (20.7 kcal/mole). Rate constants for the first order curing reaction are given. Additional studies of films cured below the ultimate T_g show that two relaxations can be observed upon heating. The first relaxation occurs near the original isothermal cure temperature with a low activation energy, about 250 kJ/mole, whereas the second relaxation occurs near the ultimate T_g, under the conditions used here, with an activation energy of 500–650 kJ/mole. It is believed that these activation energies provide a unique method of characterizing the molecular mobility of epoxy resins at various states of cure.     

Phosphorous‐containing epoxy resins from a novel synthesis route

The ? P(O)‐H in 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was used as an active group to react with the carbonyl group in 4,4′‐dihydroxybenzophenone (DHBP) to result a novel phosphorous‐containing biphenol compound (DOPO‐2OH). Phosphorous‐containing epoxy resins were therefore obtained from reacting DOPO‐2OH with epichlorohydrin or with diglycidylether bisphenol A. The synthesized compounds were characterized with FTIR, ¹H and ³¹P NMR, elemental analysis, and epoxide equivalent weight titration to demonstrate the their chemical structures. Cured epoxy resins were prepared via thermal curing the epoxy resins with various curing agents. Thermal analysis results (differential scanning calorimetry and thermogravimetric analysis) revealed that these cured epoxy resins exhibited high glass transition temperatures and high thermal stability. High char yields at 700°C and high LOI (limited oxygen index) values were also found for the cured epoxy resins to imply that the resins were possessing high flame retardancy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1697–1701, 2002     

Epoxy resin based on 4,4′-dihydroxydiphenysulfone. I. Synthesis and reaction kinetics with 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone

Epoxy resins based on 4,4′-dihydroxydiphenylsulfone (DGEBS) and diglycidyl ether of bisphenol A (DGEBA) were prepared by alkaline condensation of 4,4′-dihydroxydiphenylsulfone (bisphenol S) with epichlorohydrin and by recrystallization of liquid, commercial bisphenol A-type epoxy resin, respectively. Curing kinetics of the two epoxy compounds with 4,4′-diaminodiphenylmethane (DDM) and with 4,4′-diaminodiphenylsulfone (DDS) as well as T_g values of the cured materials were determined by the DSC method. It was found that the ? SO₂? group both in the epoxy resin and in the harener increases T_g values of the cured materials. DGEBS reacts with the used hardeners faster than does DGEBA and the curing reaction of DGEBS begins at lower temperature than does the curing reaction of DGEBA when the same amine is used. © 1994 John Wiley & Sons, Inc.     

Epoxy resin containing the poly(sily ether): Preparation,morphology, and mechanical properties

The poly(sily ether) with pendant chloromethyl groups (PSE) was synthesized by the polyaddition of dichloromethylsilane (DCM) and diglycidylether of bisphenol A (DGEBA) with tetrabutylammonium chloride (TBAC) as a catalyst. This polymer was miscible with diglycidyl ether of bisphenol A (DGEBA), the precursor of epoxy resin. The miscibility is considered to be due mainly to entropy contribution because the molecular weight of DGEBA is quite low. The blends of epoxy resin with PSE were prepared through in situ curing reaction of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐diaminodiphenylmethane (DDM) in the presence of PSE. The DDM‐cured epoxy resin/PSE blends with PSE content up to 40 wt % were obtained. The reaction started from the initial homogeneous ternary mixture of DGEBA/DDM/PSE. With curing proceeding, phase separation induced by polymerization occurred. PSE was immiscible with the 4,4′‐diaminodiphenylmethane‐cured epoxy resin (ER) because the blends exhibited two separate glass transition temperatures (T_gs) as revealed by the means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). SEM showed that all the ER/PSE blends are heterogeneous. Depending on blend composition, the blends can display PSE‐ or epoxy‐dispersed morphologies, respectively. The mechanical test showed that the DDM‐cured ER/PSE blend containing 25 wt % PSE displayed a substantial improvement in Izod impact strength, i.e., epoxy resin was significantly toughened. The improvement in impact toughness corresponded to the formation of PSE‐dispersed phase structure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 505–512, 2003     

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     

Cure kinetics of ternary blends of epoxy resins studied by nonisothermal DSC data

The curing kinetics of blends of diglycidyl ether of bisphenol A (DGEBA), cycloaliphatic epoxy resins, and carboxyl‐terminated butadiene‐acrylonitrile random copolymer (CTBN) in presence of 4,4′‐diamino diphenyl sulfone (DDS) as the curing agent was studied by nonisothermal differential scanning calorimetry (DSC) technique at different heating rates. The kinetic parameters of the curing process were determined by isoconversional method given by Malek for the kinetic analysis of the data obtained by the thermal treatment. A two‐parameter (m, n) autocatalytic model (Sestak‐Berggren equation) was found to be the most adequate selected to describe the cure kinetics of the studied epoxy resins. The values of E_a were found to be 88.6 kJ mol^?1 and 61.6 kJ mol^?1, respectively, for the studied two sample series. Nonisothermal DSC curves obtained using the experimental data show a good agreement with that theoretically calculated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Alternative monomers for 4,4′-methylenedianiline in thermosetting epoxy resins

4,4′-Methylenedianiline (MDA) is utilized to produce high temperature epoxy resins as well as other high-performance composites; however, MDA is a known carcinogen and liver toxicant. Novel dianilines derived from both petroleum and biomass with different quantities and types of methyl and methoxy substituents on the aromatic ring were prepared and studied to reduce toxicity and carcinogenic aspects of the resulting material while maintaining thermal and mechanical integrity. These dianilines were primarily prepared by coupling commercial anilines using paraformaldehyde under acidic conditions. Another dianiline was prepared by nitration of bisphenol A and subsequent reduction of the nitrates to amines. Structure–toxicity relationships indicate that multiple substituents on the aromatic ring are necessary to reduce the toxicity of the dianiline. Epoxy-amine resins were prepared by blending the dianilines with 50 wt % Epikure W liquid amine curing agent and mixing with a stoichiometric amount of EPON 828 epoxy resin. Methoxy and methyl substituents increase the melting point of the dianilines by as much as 65 °C, thereby worsening the processing of these monomers as liquid thermoset resins. Structure–property relationships show that the addition of a methoxy group to the aromatic ring and moving the amine from the 4,4′ position on the dianiline reduces the glass transition temperature (T _g) by approximately 10 °C. A single methyl group has little effect on T _g and two methyl groups increase the T _g only when both are ortho to the amine, yet this causes a large 14 °C increase in T _g. Thermal degradation profiles are not significantly affected by the dianiline. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48707.     

Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing a 4,4′‐biphenylene moiety in the backbone (Bis‐EBP) is synthesized and confirmed by elemental analysis, infrared spectroscopy, and ¹H‐nuclear magnetic resonance spectroscopy. In addition, to evaluate the influence of the 4,4′‐biphenylene group in the structure, an epoxy resin having a 1,4‐phenylene group in place of the 4,4′‐biphenylene moiety (Bis‐EP) is synthesized. The cured polymer obtained through the curing reaction between the new biphenyl‐containing epoxy resin and phenol novolac is used for making a comparison of its thermal and physical properties with those obtained from Bis‐EP and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from Bis‐EBP shows markedly higher fracture toughness of 1.32 MPa m^1/2, higher glass transition temperature, lower moisture absorption, and higher thermal decomposition temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 690–698, 1999     

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

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

Synthesis,thermal properties,and flame retardance of the epoxy‐silsesquioxane hybrid resins

Epoxy/silsesquioxane‐OH (EP‐SDOH, ED) hybrid resins were prepared from cyclohexyl‐disilanol silsesquioxane (SDOH) and diglycidyl ether of bisphenol A via the reaction between silanol and the oxirane group, with the cobalt naphthanate as a catalyst. It was found that incorporation of SDOH allows the reaction between oxirane ring and Si? OH, and the silsesquioxane cage structure can be the main chain or as the side chain of the hybrid resin. The EP‐SDOH hybrid resins with various SDOH contents were cured by 4,4′‐diaminodiphenylsulphone, and the curing reaction was investigated by differential scanning calorimetry. The curing characteristics of EP‐SDOH hybrids had been observed to be influenced by the content of SDOH in the hybrid. The differential scanning calorimetry thermograms indicated that the EP‐SDOH hybrid exhibited a higher initial temperature, peak temperature, as well as final temperature than those of the pure epoxy resin when cured by the same curing agent 4,4′‐diaminodiphenylsulphone. The curing kinetic parameters were calculated by using the Ozawa method and the results indicated that EP‐SDOH hybrids possess the same curing mechanism as the pure epoxy resin. The properties of the cured EP‐SDOH hybrid resins such as the glass transition temperature (T_g), dynamic mechanical analysis, thermal stability, as well as the flame retardance were also investigated, and the results showed that introducing silsesquioxane‐OH unit into epoxy resin successfully modified the local structure, made the chain stiffness, restrict the chain mobility, and eventually improved thermal stability and flame retardance of epoxy resin. POLYM. ENG. SCI., 47:225–234, 2007. © 2007 Society of Plastics Engineers.     

Wavelength‐shift fluorescent probes for monitoring of polymerization

The feasibility of using wavelength‐shift fluorescent probes for cure monitoring of an epoxy resin and an acrylic resin was evaluated. 4‐(N,N‐dihexylaminostyryl)‐4′‐pyridinium propylsulfonate (DHASP‐PS), as well as each of other wavelength‐shift fluorescent probes, was dissolved in the epoxy resin, a stoichiometric mixture of diglycidyl ether of bisphenol A and 4,4′‐methylene‐bis(cyclohexylamine). The fluorescence and the excitation spectra of each of the probes dissolved in the epoxy resin were then measured at various times during the cure of the epoxy resin at 60°C. The fluorescence and the excitation spectra of the probe DHASP‐PS dissolved in methyl methacrylate (MMA) were also measured at various times during the cure of the acrylic resin at 55°C. Since the peak fluorescence wavelength of each of the wavelength‐shift fluorescent probes decreased during the cure of the epoxy resin or MMA, these fluorescent probes can be used for monitoring the polymerization reactions of epoxy resins and vinyl resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 747–750, 2006     

Cure kinetics and thermal stability of micro and nanostructured thermosetting blends of epoxy resin and epoxidized styrene‐block‐butadiene‐block‐styrene triblock copolymer systems

The compatibility of styrene‐block‐butadiene‐block‐styrene (SBS) triblockcopolymer in epoxy resin is increased by the epoxidation of butadiene segment, using hydrogen peroxide in the presence of an in situ prepared catalyst in water/dichloroethane biphasic system. Highly epoxidized SBS (epoxy content SBS >26 mol%) give rise to nanostructured blends with epoxy resin. The cure kinetics of micro and nanostructured blends of epoxy resin [diglycidyl ether of bisphenol A; (DGEBA)]/amine curing agent [4,4′‐diaminodiphenylmethane (DDM)] with epoxidized styrene‐block‐butadiene‐block‐styrene (eSBS 47 mol%) triblock copolymer has been studied for the first time using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as kinetic constants and activation energy. The cure reaction rate is decreased with increasing the concentration of eSBS in the blends and also with the lowering of cure temperature. The compatibility of eSBS in epoxy resin is investigated in detailed by Fourier transform infrared spectroscopy, optical and transmition electron microscopic analysis. The experimental data of the cure behavior for the systems, epoxy/DDM and epoxy/eSBS(47 mol%)/DDM show an autocatalytic behavior regardless of the presence of eSBS in agreement with Kamal's model. The thermal stability of cured resins is also evaluated using thermogravimetry in nitrogen atmosphere. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Polydimethylsiloxane containing isocyanate group-modified epoxy resin: Curing,characterization, and properties

A synthesized polydimethylsiloxane containing an isocyanate group was used to improve the flexibility and to reduce the internal stress of epoxy resin cured with MDA (4,4′-methylene dianiline). The effect of polysiloxane content on the curing kinetics of a novolac-type epoxy modified with an isocyanate group was investigated. It was found that the modified epoxy resin showed significant improvement in impact strength. The polysiloxane containing isocyanate groups effectively depressed the internal stress of cured epoxy resins by reducing the flexural modulus and the coefficient of thermal expansion, while the glass transition temperature was increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2739–2747, 1999     

Preparation and curing kinetics of bisphenol A type novolac epoxy resins

A bisphenol A type novolac resin (Bis‐ANR) was synthesized from bisphenol A and formaldehyde; the resulting novolac was epoxidized to generate a bisphenol A type novolac epoxy resin (Bis‐ANER). The chemical structures of Bis‐ANR and Bis‐ANER were confirmed by ¹H‐NMR spectroscopy and IR spectroscopy; the molecular weights and molecular weight distributions were determined by gel permeation chromatography. In addition, the curing process of Bis‐ANER with 4,4′‐diaminodiphenyl sulfone was studied in both dynamic and isothermal modes with differential scanning calorimetry. The dynamic curing kinetic analysis was evaluated with both the Kissinger and Flynn–Wall–Ozawa methods, and the curing activation energy values were obtained. The isothermal curing reaction exhibited autocatalytic behavior, and the curing kinetics were described with the Kamal kinetics model, which accounted for both the autocatalytic and diffusion‐control effects. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 858–868, 2006     

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     

Epoxy resins based on aromatic glycidylamines. VI. Toughening of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane by reactive additives

Mechanical properties of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane and its mixtures with liquid bisphenol A-type epoxy resins, bisphenol A and ε-caprolactone have been studied. 4,4′-Diaminodiphenylsulfone was used as hardener. Materials with improved fracture toughness and good mechanical strength in the temperature range 20–200°C have been formulated.     

Synthesis and properties of novel phosphorus‐containing bismaleimide/epoxy resins

A novel soluble phosphorus‐containing bismaleimide (BMI) monomer, bis(3‐maleimidophenyl)phenylphosphine oxide (BMIPO), was synthesized by the imidization of bis(3‐aminophenyl) phenylphosphine oxide, in which its structural characterization was identified with ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectra. The BMIPO resin, with five‐membered imide rings and high phenyl density, was an excellent flame retardant with a high glass‐transition temperature (T_g), onset decomposition temperature, and limited oxygen index. In phosphorus‐containing BMI/epoxy/4,4′‐methylene dianiline (DDM)‐cured resins, homogeneous products were obtained from all proportions without phase separation. Because of the higher reactivity of BMIPO/DDM relative to that of 4,4′‐bismaleimidodiphenylmethane (BMIM)/DDM, the increase in the BMIPO/BMIM ratio in this blending resin increased the recrosslinking hazards of the postcuring stage and so lowered the T_g value and thermal stability. The thermal stability of the BMI/epoxy‐cured system was lower than that of the epoxy‐cured system because of the introduction of a phosphide group into BMIPO, whereas for the T_g value and flame retardancy, the former was significantly higher than the latter: the higher the BMIPO content in the blend, the higher the flame retardancy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2080–2089, 2002; DOI 10.1002/app.10607     

Cure kinetics and thermal properties of tetramethylbiphenyl epoxy resin/phthalazinone‐containing diamine/hexa(phenoxy)cyclotriphophazene system

Inherently flame retardant epoxy resin is a kind of halogen‐free material for making high‐performance electronic materials. This work describes an inherently flame retardant epoxy system composed of 4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP), 1,2‐dihydro‐2‐(4‐aminophenyl)‐4‐(4‐(4‐aminophenoxy) phenyl) (2H) phthalazin‐1‐one (DAP), and hexa(phenoxy) cyclotriphophazene (HPCTP). The cure kinetics of TMBP/DAP in the presence or absence of HPCTP were investigated using isoconversional method by means of nonisothermal differential scanning calorimeter (DSC). Kinetic analysis results indicated that the effective activation energy (E_α) decreased with increasing the extent of conversion (α) for TMBP/DAP system because diffusion‐controlled reaction dominated the curing reaction gradually in the later cure stage. TMBP/DAP/HPCTP(10 wt %) system had higher E_α values than those of TMBP/DAP system in the early cure stage (α < 0.35), and an increase phenomenon of E_α ～ α dependence in the later cure stage (α ≥ 0.60) due to kinetic‐controlled reaction in the later cure stage. Such complex E_α ～ α dependence of TMBP/DAP/HPCTP(10 wt %) system might be associated with the change of the physical state (mainly viscosity) of the curing system due to the introduction of HPCTP. These cured epoxy resins had very high glass transition temperatures (202–235°C), excellent thermal stability with high 5 wt % decomposition temperatures (>340°C) and high char yields (>25.6 wt %). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009