Preparation and properties of epoxy/phenol formaldehyde novolac/hexakis(methoxymethyl)melamine hybrid resins from in situ polymerization

Based on the self‐condensation of hexakis(methoxymethyl)melamine (HMMM), the condensation between HMMM and phenol formaldehyde novolac resin (n‐PF), and the addition reaction of diglycidyl ether of biphenyl A (DGEBA) and n‐PF, a homogeneous, transparent hybrid thermoset was prepared via in situ polymerization of DGEBA, n‐PF, and HMMM. No phase separations were observed even for the DGEBA/n‐PF/HMMM hybrid thermoset containing 40 wt % HMMM. These hybrid thermosets had high glass‐transition temperatures (98–127°C from differential scanning calorimetry and 111–138°C from dynamic mechanical analysis), excellent thermal stability with high 5 wt % decomposition temperatures (>322°C), high char yields (>24 wt %), and improved flame retardancy with high limited oxygen indices (>28.5). The excellent overall properties of these hybrid resins may lead to their applications in high‐performance “green” electronic products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Epoxy toughening using low viscosity liquid diglycidyl ether of ethoxylated bisphenol‐A

Two new epoxy resins, diglycidyl ether of ethoxylated bisphenol‐A (BPA) with two and six oxyethylene units (DGEBAEO‐2 and DGEBAEO‐6) were synthesized and characterized. DGEBAEO‐6 was used to toughen the conventional epoxy resin diglycidyl ether of BPA (DGEBA). The blends of DGEBA with different amounts of DGEBAEO‐6 were cured by 4,4′‐diamino diphenylmethane (DDM), and their thermal and mechanical properties were examined. The DSC and DMA results presented that DGEBA/DGEBAEO‐6 blends exhibited a homogenous phase, and the glass transition temperature of the blends was inversely proportional to the content of DGEBAEO‐6. The impact strength of the cured blends was directly proportional to the content of DGEBAEO‐6, and reached five times higher than that of the neat DGEBA when 50 wt % DGEBAEO‐6 was used; the same impact strength was achieved for DDM‐cured DGEBAEO‐2. The viscosities of the blends decreased with increasing the DGEBAEO‐6 content, whereas the tensile and flexural strength and the thermal stabilities were not obviously affected. Scanning electron microscopic results confirmed that the plastic deformation inducing by the incorporated flexible oxyethylene units was responsible for the toughness improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel adamantane‐containing epoxy resin

A novel adamantane‐containing epoxy resin diglycidyl ether of bisphenol‐adamantane (DGEBAda) was successfully synthesized from 1,3‐bis(4‐hydroxyphenyl)adamantane by a one‐step method. The proposed structure of the epoxy resin was confirmed with Fourier transform infrared, ¹H‐NMR, gel permeation chromatography, and epoxy equivalent weight titration. The synthesized adamantane‐containing epoxy resin was cured with 4,4′‐diaminodiphenyl sulfone (DDS) and dicyandiamide (DICY). The thermal properties of the DDS‐cured epoxy were investigated with differential scanning calorimetry and thermogravimetric analysis (TGA). The dielectric properties of the DICY‐cured epoxy were determined from its dielectric spectrum. The obtained results were compared with those of commercially available diglycidyl ether of bisphenol A (DGEBA), a tetramethyl biphenol (TMBP)/epoxy system, and some other associated epoxy resins. According to the measured values, the glass‐transition temperature of the DGEBAda/DDS system (223°C) was higher than that of the DGEBA/DDS system and close to that of the TMBP/DDS system. TGA results showed that the DGEBAda/DDS system had a higher char yield (25.02%) and integral procedure decomposition temperature (850.7°C); however, the 5 wt % degradation temperature was lower than that of DDS‐cured DGEBA and TMBP. Moreover, DGEBAda/DDS had reduced moisture absorption and lower dielectric properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of wood‐based epoxy resins and their mechanical and adhesive properties

Wood‐based epoxy resins were synthesized from resorcinol‐liquefied wood. Wood was first liquefied in the presence of resorcinol with or without a sulfuric acid catalyst at high temperature. Because of the hydroxyl groups, the resorcinol‐liquefied wood was considered as a precursor for synthesizing wood‐based epoxy resin. Namely, the phenolic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition. By the glycidyl etherification, epoxy functionality was introduced to the liquefied wood. The epoxy functionality of the resins was controlled by the concentration of phenolic OH groups in the liquefied wood, which would be a dominant factor for crosslink density and properties of the cured epoxy resins. The flexural strength (150–180 MPa) and the modulus of elasticity (3.2 GPa) of the highly crosslinked wood‐based epoxy resin were equivalent to those of the commercially available epoxy resin, diglycidyl ether of bisphenol A (DGEBA). Also, the shear adhesive strength of the wood‐based epoxy resin was higher than that of DGEBA when plywood was used as the adhesive substrates. The mechanical and adhesive properties suggested that the wood‐based epoxy resins would be well suited for matrix resins of natural plant‐fiber reinforced composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2285–2292, 2006     

Preparation of hyperbranched epoxy resin containing nitrogen heterocycle and its toughened and reinforced composites

Low‐viscosity hyperbranched epoxy resin‐containing nitrogen heterocycle (HTPE) is synthesized from epichlorohydrin (ECH), dimethylol propionic acid (DMPA), and tris(2‐hydrooxyethyl)‐isocyanurate. The structure and properties of HTPE are characterized by FTIR, GPC, and molecular simulation. The performance of HTPE/diglycidyl ether of bisphenol‐A (DGEBA) composites first increase and then decrease with the increase of the content and molecular weight of HTPE. Compared to those of pure DGEBA, the impact strength, fracture toughness, tensile, and flexural strength of HTPE‐2/DGEBA composite can be enhanced by about 192%, 39%, 18%, and 23%, respectively. The absence of microphase separation and the presence of lots of “protonema” on the fracture surface of the composites are explicated by an in situ reinforcing and toughening mechanism. The intramolecular cavity of HTPE and the strong interaction between HTPE and DGEBA are two key factors to toughening and reinforcing DGEBA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

Effect of backbone moiety in epoxies on thermal conductivity of epoxy/alumina composite

We chose two commercial epoxies, bisphenol A diglycidyl ether (DGEBA) and 3,3′,5,5′‐tetramethyl‐4,4′‐biphenol diglycidyl ether (TMBP), and synthesized one liquid crystalline epoxy (LCE), 4′4′‐bis(4‐hydroxybenzylidene)‐diaminophenylene diglycidyl ether (LCE‐DP) to investigate the effect of backbone moiety in epoxies on the thermal conductivity of epoxy/alumina composite. The DGEBA structure shows an amorphous state and the TMBP structure displays a crystal phase, whereas the LCE‐DP structure exhibits a liquid crystalline phase. The curing behaviors of them were examined employing 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent. The heat of curing of epoxy resin was measured with dynamic differential scanning calorimetry (DSC). Alumina (Al₂O₃) of commercial source was applied as an inorganic filler. Thermal conductivity was measured by laser flash method and compared with value predicted by two theoretical models, Lewis‐Nielsen and Agari‐Uno. The results indicated that the thermal conductivity of the LCE‐DP structure was larger than that of the commercial epoxy resins such as TMBP and DGEBA and the experimental data fitted quite well in the values estimated by Agari‐Uno model. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

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     

Synthesis and characterization of a high refractive diglycidyl ether of thiodibenzenethiol epoxy resin

High refractive index of epoxy resins used as encapsulant in light-emitting diode (LED) is essential in improving the light extraction efficiency, reducing heat and prolonging the service life of LED packages. In this study, diglycidyl ether of thiodibenzenethiol (DGETDBT), an epoxy resin with high refractive index, was synthesized via a novel method and its chemical structure was characterized with Fourier-transform infrared (FTIR) spectrometer and ¹H NMR spectrometer. Using m-xylylenediamine (MXDA) as curing agent, the curing behavior of DGETDBT was studied by differential scanning calorimetry (DSC) and was compared with that of diglycidyl ether of bisphenol A (DGEBA), a generally used encapsulant in LED. The thermal behavior and optical performance of these two resins were investigated with thermogravimetric analyses, UV?CVis scanning spectrophotometer, and Abbe refractometer, respectively. The results showed that DGETDBT/MXDA resin demonstrated similar curing and thermal behavior to DGEBA/MXDA resin. But its refractive index reaches 1.698, which is significantly higher than that of DGEBA/MXDA resin (1.604). Comparatively, DGETDBT resin can be expected to be a more effective encapsulant of LED.     

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     

Mechanical and dynamic mechanical properties of jute fibers–Novolac–epoxy composite laminates

A study was done of jute composite using a polymer matrix of epoxidized Novolac resin (ENR), diglycidyl ether of bisphenol A (DGEBA)–based epoxy, and their blends with different weight percentages of the resins. It was found that on blending ENR with DGEBA, the storage modulii at room temperature are enhanced by about 100% or more in the case of 30 and 40% ENR‐containing matrices, whereas the enhancement in the case of 20 and 12% ENR‐containing matrices is only 50% that of the pure matrix. It was also observed that the tan δ peak heights of the composites containing 30 and 40% ENR are closer to that of 20% ENR‐containing composite. The probable explanation drawn on the basis of experimental findings of DMA and mechanical analysis is that by blending ENR with DGEBA epoxy it is possible to manufacture jute composites with increased stiffness without sacrificing their ductility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2800–2807, 2002     

High performance modification of hyperbranched polyborate on diglycidyl ether of bisphenol‐a resin

High performance epoxy resin was obtained by introducing hyperbranched polyborate (HBPB) into diglycidyl ether of bisphenol A (DGEBA) resin to overcome the defects such as low char yield and poor toughness of DGEBA resin. By virtue of the massive functional end groups, hyperbranched and rigid boron‐containing structures of HBPB, the thermal resistance of DGEBA resin cured with diamino diphenyl sulfone (DDS) can be greatly improved. Moreover, with the toughening effect of hyperbranched structures of HBPB, the mechanical properties such as flexural strength and interlaminar shear strength of the carbon fiber reinforced DGEBA‐DDS composite could be greatly increased by HBPB without a decrease on modulus and glass transition temperature of DGEBA‐DDS resin. POLYM. COMPOS. 36:424–432, 2015. © 2014 Society of Plastics Engineers     

Polymerization of an epoxy resin modified with azobenzene groups monitored by near‐infrared spectroscopy

New photosensitive materials containing photochromic azobenzene moieties were synthesized. For this purpose, an epoxy resin based on diglycidyl ether of bisphenol A (DGEBA) was reacted with an azobenzene chromophore (disperse orange 3, AZ) to satisfactorily synthesize an azo‐modified prepolymer, which was then used to generate series of epoxy‐based polymers containing azo groups. Three different amines were used as hardeners, with the aim of obtaining materials with different chemical structures. Understanding the epoxy resin polymerization kinetics is essential for intelligent processing of materials. Near‐IR (NIR) spectral analysis was used to follow the polymerization kinetics. The quality of the NIR spectra enables concentrations of individual chemical species to be measured in real time. Conversion of epoxy and primary amine groups, as well as the concentration of different groups, as a function of reaction time was therefore calculated by this spectroscopic technique. Samples containing azo units were compared to the pure DGEBA/amine systems. Results showed that the azo‐prepolymer incorporation has an accelerating effect on polymerization rate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and Properties of a Novel Flame-Retardant Epoxy Resin Containing Biphenylyl/Phenyl Phosphonic Moieties

A novel reactive diol, bis-biphenyloxy (4-hydroxy) phenyl phosphine oxide (BBPHPPO) which contains both biphenylyl and phenyl phosphonic groups was synthesized. Flame retardant advanced epoxy resin was obtained by chain extension of diglycidyl ether of bisphenol-A (DGEBA) with the phosphorus-containing diol (BBPHPPO). The thermal properties and flame retardancy of cured epoxy resin were studied. The resulting BBPHPPO containing epoxy system exhibited higher glass transition temperature than that of advanced epoxy resins prepared from bisphenol-A (BA) and tetrabromobisphenol-A (TBBA). The high char yield and the high LOI value were observed to prove the excellent flame retardancy of this phosphorus-containing epoxy resin.     

Effects of particle size and rubber content on fracture toughness in rubber-modified epoxies

The effects of particle size of core-shell rubber on the fracture toughness of rubber-modified epoxies were investigated. Various sizes of core-shell rubber particles, from 0.16 to 1.2 μm in diameter, were synthesized by seeded emulsion polymerization. Particle size effects were clearly seen for lower crosslinked diglycidyl ether of bisphenol A (DGEBA)/piperidine resin. Fracture toughness increased as the particle size of core-shell rubber decreased from 1.2 to 0.4 μm. On the other hand, fracture toughness was constant in this range of particle sizes for higher crosslinked DGEBA/diaminodiphenylmethane (DDM) resin. Cavitation in the rubbery core and shear deformation in the matrix are the toughening mechanisms for DGEBA/piperidine resin, whereas cavitation is the only mechanism for DGEBA/DDM resin. Toughening effectiveness decreased with <0.2 μm core-shell rubber particles since they are difficult to cavitate. The effects of core-shell rubber content on fracture toughness of rubber-modified epoxies were also examined. The optimum rubber content for maximum toughness of rubber-modified epoxies decreased with decreased particle size of core-shell rubber in shear deformable DGEBA/piperidine resin. But the fracture toughness of rubber-modified DGEBA/DDM resins increased as the rubber content increased.     

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.     

Effect of Phenol/Formaldehyde Stoichiometry on the Modification of Epoxy Resin Using Epoxidized Novolacs

ABSTRACT

Unmodified epoxy resins based on bisphenol A exhibit brittleness and low elongation after cure. This article reports the results of a study for improving the properties of epoxy resin by blending with suitable thermosets. Hybrid polymer networks of diglycidyl ether of bisphenol A (DGEBA) resin with epoxidized phenolic novolac resins (EPN) containing phenol and formaldehyde in different stoichiometric ratios were prepared by physical blending. The modified epoxy resins were found to exhibit improved mechanical and thermal properties compared to the neat resin. DGEBA resins containing 2.5 to 20 wt% of epoxidized novolac resins (EPN) prepared in various stoichiometric ratios (1:0.6, 1:0.7, 1:08, and 1:0.9) between phenol and formaldehyde were cured using a room temperature amine hardener. The cured samples were tested for mechanical properties such as tensile strength, modulus, elongation, and energy absorption at break. All the EPNs are seen to improve tensile strength, elongation, and energy absorption at break of the resin. The blend of DGEBA with 10 wt% of EPN-3 (1:0.8) exhibits maximum improvement in strength, elongation, and energy absorption. EPN loading above 10 wt% is found to lower these properties in a manner similar to the behavior of any filler material. The property profiles of epoxy–EPN blends imply a toughening action by epoxidized novolac resins and the extent of modification is found to depend on the molar ratio between phenol and formaldehyde in the novolac.     

Effect of microencapsulated curing agents on the curing behavior for diglycidyl ether of bisphenol A epoxy resin systems

Microcapsules containing a curing agent, 2‐phenyl imidazole (2PZ), for a diglycidyl ether of bisphenol A (DGEBA) epoxy resin were prepared by a solid‐in‐oil‐in‐water emulsion solvent evaporation technique with poly(methyl methacrylate) (PMMA) as a polymeric wall. The mean particle size of the microcapsules and the concentration of 2PZ were about 10 μm and nearly 10 wt %, respectively. The onset cure temperature and peak temperature of the DGEBA/2PZ–PMMA microcapsule system appeared to increase by nearly 30 and 10°C, respectively, versus those of the DGEBA/2PZ system because of the increased reaction energy of curing. The former could take more than 3 months at room temperature, whereas the latter was cured after only a week. The values of the reaction order (a curing kinetic parameter) for DGEBA/2PZ and DGEBA/2PZ–PMMA microcapsules were quite close, and this showed that the curing reactions of the two samples proceeded conformably. The curing mechanism was investigated, and a two‐step initiation mechanism was considered: the first was assigned to adduct formation, whereas the second was due to alkoxide‐initiated polymerization. The glass‐transition temperature of DGEBA/2PZ was 165.2°C, nearly 20°C higher than the glass‐transition temperatures of DGEBA/2PZ–PMMA microcapsules and DGEBA/2PZ/PMMA microspheres, as determined by differential scanning calorimetry measurements. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin

A novel nitrogen‐containing cyclic phosphate (NDP) was synthesized and well characterized by ¹H, ¹³C, ³¹P NMR, mass spectra and elemental analysis. NDP was used as an additive intumescent flame retardant (AIFR) to impart flame retardancy and dripping resistance for diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) curied by 4,4′‐diaminodiphenylsulfone (DDS) with different phosphorus content. The flammability, thermal stability, and mechanical properties of NDP modified DGEBA/DDS thermosets were investigated by UL‐94 vertical burning test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Izod impact strength and flexural property tests. The results showed that NDP modified DGEBA/DDS thermosets exhibited excellent flame retardancy, moderate changes in glass transition temperature and thermal stability. When the phosphorus content reached only 1.5 wt %, the NDP modified DGEBA/DDS thermoset could result in satisfied flame retardancy (UL‐94, V‐0). The TGA curves under nitrogen and air atmosphere suggested that NDP had good ability of char formation, and there existed a distinct synergistic effect between phosphorus and nitrogen. The flame retardant mechanism was further realized by studying the structure and morphology of char residues using FT‐IR and scanning electron microscopy (SEM). It indicated that NDP as phosphorus‐nitrogen containing flame retardant worked by both of the condensed phase action and the vapor phase action. Additionally, the addition of NDP decreased slightly the flexural strength of the flame retarded DGEBA epoxy resins, and increased the Izod impact strength of these thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41859.