Synthesis,thermal properties,and flame retardance of phosphorus‐containing epoxy‐silica hybrid resins

A novel epoxy resin modifier, phosphorus‐containing epoxide siloxane (DPS) with cyclic phosphorus groups in the Si O network, was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) with polyhedral‐oligomeric siloxanes, which was synthesized by the sol–gel reaction of 3‐glycidoxypropyltrimethoxysilane. DPS was confirmed by Fourier transform infrared and ²⁹Si NMR measurement, and then was employed to modify epoxy resin at various ratios, with 4,4‐diaminodiphenyl‐methane as a curing agent. In order to make a comparison, DOPO‐containing epoxy resins were also cured under the same conditions. The resulting organic–inorganic hybrid epoxy resins modified with DPS exhibited a high glass transition temperature (T_g), a good thermal stability, and a high limited oxygen index. In addition, the tensile strength of cured products was also rather desirable. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

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     

Toughening of epoxy resins by hydroxy‐terminated,silicon‐modified polyurethane oligomers

Epoxy resins are among the most versatile engineering structural materials. A wide variety of epoxy resins are commercially available, but most are brittle. Several approaches have been used to improve the toughness of epoxy resins, including the addition of fillers, rubber particles, thermoplastics, and their hybrids, as well as interpenetrating polymer networks (IPNs) of acrylic, polyurethane, and flexibilizers such as polyols. This last approach has not received much attention; none of them have been able to suitably increase resin toughness with out sacrificing tensile properties. Therefore, in an attempt to fill this gap, we experimented with newly synthesized hydroxy‐terminated silicon‐modified polyurethane (SiMPU) oligomers as toughening agents for epoxy resins. SiMPU oligomers were synthesized from dimethyl dichlorosilane, poly(ethylene glycol) (weight‐average molecular weight ～ 200), and toluene 2,4‐diisocyanate and characterized with IR, ¹H‐NMR and ¹³C‐NMR, and gel permeation chromatography. The synthesized SiMPU oligomers, with different concentrations, formed IPNs within the epoxy resins (diglycidyl ether of bisphenol A). The resultant IPN products were cured with diaminodiphenyl sulfone, diaminodiphenyl ether, and a Ciba–Geigy hardener under various curing conditions. Various mechanical properties, including the lap‐shear, peel, and impact strength, were evaluated. The results showed that 15 phr SiMPU led to better impact strength of epoxy resins than the others without the deterioration of the tensile properties. The impact strength increased continuously and reached a maximum value (five times greater than that of the virgin resin) at a critical modifier concentration (20 phr). The critical stress intensity factor reached 3.0 MPa m^1/2 (it was only 0.95 MPa m^1/2 for the virgin resin). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1497–1506, 2003     

The conductivity behavior of multi‐component epoxy,metal particle,carbon black,carbon fibril composites

Following the previous studies of epoxy/silver conductive composites, a detailed investigation of the influence of ethylene glycol on the resulting resistivity of various composites was carried out. Ethylene glycol was found to have a catalytic effect on the curing process of the epoxy resin, verified by differential scanning calorimetry studies. The accelerated curing process diminishes settling of the metal particles and therefore results in better and more uniform conductivities. High temperature curing of the composites was found to have a similar effect on the conductivity. The conductivity behavior of some other composites, such as epoxy/nickel, epoxy/nickel/carbon fibrils, and epoxy/carbon black/carbon fibrils, were also studied. The structure–property relations were better understood through scanning electron microscopy observations. Silver and nickel particles were found to perform differently in the cured epoxy, showing different percolation concentrations and conductivity levels. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1706–1713, 2002     

Curing behavior of epoxy/POSS/DDS hybrid systems

The curing behavior of a difunctional epoxy resin/octa(aminopropyl)silsesquioxanes hybrid resin system using 4,4′′‐diaminodiphenyl sulfone as curing agent was studied. Fourier transform infrared (FTIR) spectroscopy was used to evidence the formation of the hybrid resin and to monitor the curing process. Results showed that the reactivity of the hybrid resin system was slightly lower than that of the pristine epoxy resin. Differential scanning calorimetry was used to study the curing kinetics of the hybrid resin. The curing kinetics of the pristine and hybrid resins was analyzed by two methods: Kissinger and Flynn‐Wall‐Ozawa methods. The FTIR analysis accorded well with the results of the kinetics study. POLYM. COMPOS., 29:77–83, 2008. © 2007 Society of Plastics Engineers     

Epoxy‐tert‐butyl poly(cyanoarylene ether) blends: Phase morphology,fracture toughness,and mechanical properties

Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–unsaturated polyester modified epoxy intercrosslinked matrices

An intercrosslinked network of unsaturated polyester–bismaleimide modified epoxy matrix systems was developed. Epoxy systems modified with 10, 20, and 30% (by weight) of unsaturated polyester were made by using epoxy resin and unsaturated polyester with benzoyl peroxide and diaminodiphenylmethane as curing agents. The reaction between unsaturated polyester and epoxy resin was confirmed by IR spectral studies. The unsaturated polyester toughened epoxy systems were further modified with 5, 10, and 15% (by weightt) of bismaleimide (BMI). The matrices, in the form of castings, were characterized for their mechanical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the matrix samples were performed to determine the glass transition temperature (T_g) and thermal degradation temperature of the systems, respectively. Mechanical properties, viz: tensile strength, flexural strength, and plain strain fracture toughness of intercrosslinked epoxy systems, were studied by ASTM methods. Data obtained from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improves toughness but with a reduction in glass transition, whereas the incorporation of bismaleimide into epoxy resin improved both mechanical strength and thermal behavior of epoxy resin. The introduction of bismaleimide into unsaturated polyester‐modified epoxy resin altered thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2853–2861, 2002     

Synthesis,characterization, and curing of {2,6–bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA)

The curing behavior of epoxy resin prepared by reacting epichlorohydrin with amine functional aniline acetaldehyde condensate (AFAAC) was investigated using AFAAC as a curing agent. The epoxy resin, {2,6‐bis‐[2‐(bis‐oxiranylmethyl‐amino)‐methylbenzyl]‐phenyl}‐bis‐oxiranylmethylamine (BPBOMA), was characterized by FTIR and ¹H‐NMR spectroscopy, viscosity measurement, and determination of epoxy content. Analysis of the curing reaction was followed by differential scanning calorimetry (DSC) analysis. To investigate the curing kinetic with AFAAC, dynamic DSC scans were made at heating rates of 5, 10, 15, and 20°C/min. The activation energy and frequency factor of the AFAAC formulation were evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3168–3174, 2006     

Synthesis and properties of phosphorus‐containing advanced epoxy resins. II

Two phosphorus‐containing diacids were synthesized from 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and either maleic acid or itaconic acid and then reacted with diglycidyl ether of bisphenol A (DGEBA) to form two series of advanced epoxy resins. Reaction conditions, such as reaction time, temperature and catalyst, are discussed in this article. After curing with 4,4'‐diaminodiphenyl sulfone (DDS), thermal properties of cured epoxy resins were studied using dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was evaluated using a UL‐94 measurement. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 228–235, 2000     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Kinetic approach for epoxy resins cured with diaminodiphenyl sulfone under non‐isothermal conditions

The curing reactions of epoxy resin basing on diglycidyl ether bisphenol A (DGEBA) with 4,4′‐diaminodiphenyl sulfone (DDS) were investigated with a differential scanning calorimeter and gel permeation chromatography. Based on the generating function method and the Monte Carlo simulation procedure, kinetic models for both isothermal and nonisothermal curing conditions were proposed. The apparent activation energy of curing reactions was found to be 14.9 Kcal/mol by the thermal analysis. According to our kinetic models, gel points, the profiles of epoxy conversion, and the molecular weights of polymers were calculated. Good agreement is obtained between the model predictions and experimental data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 721–728, 1999     

Preparation of 4‐(4‐hydroxyphenoxy)phenol diglycidyl ether with improved toughness behavior

A high‐performance difunctional epoxy resin, 4‐(4‐hydroxyphenoxy)phenol diglycidyl ether (DHPOP), was synthesized by a two‐step method. The curing behavior of DHPOP was investigated by nonisothermal differential scanning calorimetry method and the curing kinetics results revealed that the introduction of ether linkage could improve the activity of epoxy groups, leading to a lower curing temperature and apparent activation energy compared with that of the commercial bisphenol‐A diglycidyl ether (DGEBA). A series of copolymers were then prepared by varying the mass ratio of DHPOP and DGEBA, which were cured with 4,4′‐diaminodiphenyl methane. The effect of DHPOP contents on thermal and mechanical properties and fracture morphology was studied. As expected, with the increase of DHPOP in the network, the impact strength and char yield were significantly enhanced, while the glass transition temperature (T_g) remained unchanged because of the increase of crosslink density. The excellent toughness endows the DHPOP with the promising potential for the application as high‐performance resin matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46458.     

An epoxy-terminated structural adhesive. II. Curing,adhesive strength,and flammability characteristics

Curing characteristics and the curing schedule of an epoxy-terminated polymer (ETP) were investigated using diaminodiphenyl ether (DADPE), diaminodiphenyl sulfone (DADPS), diaminodiphenyl methane (DADPM), and the hardener of a commercial epoxy, two-pack Araldite (Ciba-Geigy), as curing agents. The adhesive strength of the ETP was measured by various ASTM methods like lap-shear, cohesion, and adhesion tests on metal-metal, wood-metal, wood-wood, and metal-polymer interfaces. All these results are compared with Araldite GY250, a two-pack Araldite (Ciba-Geigy). The flame retardancy of virgin ETP, ETP-Araldite GY250 blends, and various commercial-grade fire-resistant epoxies was measured. A structure flammability correlation for the ETP-Araldite GY250 blends is also reported.     

Natural fiber composites of high‐temperature thermoplastic polymers: Effects of coupling agents

Our earlier paper (Jana, S.C.; Prieto, A. J Appl Polym Sci 2002, 86, 2159) on the development of natural fiber composites of high‐performance thermoplastic polymers described a new methodology for the manufacturing of composite materials of a high‐temperature thermoplastic polymer, poly(phenylene ether) (PPE) and wood flour, a cellulosic natural filler. A thermosetting epoxy, used as a reactive solvent, reduced the processing temperature of PPE/epoxy blends to well below the decomposition temperature of natural fillers. In addition, the epoxy component, upon polymerization, formed coating layers around the filler particles to provide resistance against moisture diffusion and attacks by acids and alkali. This article describes the results of an investigation on two outstanding issues: (1) the influence of cellulosic wood particles and coupling agents on the speed of epoxy curing and reaction‐induced phase separation and (2) the effects of coupling agents on the morphology of crosslinked epoxy at the surfaces of natural fillers and mechanical properties of the composites. It was found that wood particles expedited epoxy curing in the composites; the extent of epoxy curing, however, was reduced in the presence of coupling agents. Also, the coupling agents promoted complete coverage of wood flour particles by polymerized epoxy, although the mechanical properties deteriorated over systems without coupling agents. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2168–2173, 2002     

Synthesis and characterization of emulsion‐type curing agent of water‐borne epoxy resin

Self‐emulsified water‐borne epoxy curing agent of nonionic type was prepared using triethylene tetramine (TETA) and derivative of epoxy resin as a capping agent, which was synthesized by liquid epoxy resin (E51) and polyethylene glycol (PEG), and the curing agent possessed emulsification and curing properties at the same time. The curing agent with good property of emulsifying liquid epoxy resin could be obtained under the condition of the molar ratio of PEG : E51 : TETA as 0.8 : 1 : 3.5 at 80°C for 5 h. The mean particle size of the emulsion liquid was about 220 nm with the prepared curing agent and epoxy resin at the mass ratio of 1 : 3. The structure of the emulsion‐type curing agent was confirmed by FTIR and ¹H NMR spectra, and the mechanism of cured film formation was also analyzed by SEM photographs. The cured film prepared by the emulsion‐type curing agent and epoxy resin under ambient cure conditions showed good properties even at high staving temperature. This study provides useful suggestions for the application of the water‐borne epoxy resins in coating industry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2652–2659, 2013     

Low dielectric thermoset. I. Synthesis and properties of novel 2,6‐dimethyl phenol‐dicyclopentadiene epoxy

A 2,6‐dimethyl phenol‐dicyclopentadiene novolac was synthesized from dicyclopentadiene and 2,6‐dimethyl phenol, and the resultant 2,6‐dimethyl phenol‐dicyclopentadiene novolac was epoxidized to 2,6‐dimethyl phenol‐dicyclopentadiene epoxy. The structures of novolac and epoxy were confirmed by Fourier transform infrared spectroscopy (FTIR), elemental analysis, mass spectroscopy (MS), nuclear magnetic resonance spectroscopy (NMR), and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol‐dicyclopentadiene epoxy was then cured with 4,4‐diaminodiphenyl methane (DDM), phenol novolac (PN), 4,4‐diaminodiphenyl sulfone (DDS), and 4,4‐diaminodiphenyl ether (DDE). Thermal properties of cured epoxy resins were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric analysis (DEA), and thermal gravimetric analysis (TGA). These data were compared with those of the commercial bisphenol A epoxy system. Compared with the bisphenol A epoxy system, the cured 2,6‐dimethyl phenol‐ dicyclopentadiene epoxy resins exhibited lower dielectric constants (～3.0 at 1 MHz and 2.8 at 1 GHz), dissipation factors (～0.007 at 1 MHz and 0.004 at 1 GHz), glass transition temperatures (140–188°C), thermal stability (5% degradation temperature at 382–404°C), thermal expansion coefficients [50–60 ppm/°C before glass‐transition temperature (T_g)], and moisture absorption (0.9–1.1%), but higher modulus (～2 Gpa at 60°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2607–2613, 2003     

Curing characteristics of epoxy resin systems that include a biphenyl moiety

The curing characteristics of epoxy resin systems that include a biphenyl moiety were investigated according to the change of curing agents. Their curing kinetics mainly depend on the type of hardener. An autocatalytic kinetic reaction occurs in epoxy resin systems with phenol novolac hardener, regardless of the kinds of epoxy resin and the epoxy resin systems using Xylok and DCPDP (dicyclopentadiene‐type phenol resin) curing agents following an nth‐order kinetic mechanism. The kinetic parameters of all epoxy resin systems were reported in terms of a generalized kinetic equation that considered the diffusion term. The fastest reaction conversion rate among the epoxy resin systems with a phenol novolac curing agent was obtained in the EOCN‐C epoxy resin system, and for systems with Xylok and DCPDP hardeners, the highest reaction rate values were obtained in NC‐3000P and EOCN‐C epoxy resin systems, respectively. The system constants in DiBenedetto's equation of each epoxy resin system with different curing agents were obtained, and their curing characteristics can be interpreted by the curing model using a curing agent as a spacer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1942–1952, 2002     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445     

Morphology,viscoelastic properties,and mechanical behavior of epoxy resin modified with hydroxyl‐terminated poly(ether ether ketone) oligomer with pendent tert‐butyl groups

Hydroxyl‐terminated poly (ether ether ketone) with pendent tert‐butyl groups (PEEKTOH) synthesized from 4,4′‐difluorobenzophenone and tert‐butyl hydroquinone was blended with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin. A diamine, 4,4′‐diaminodiphenyl sulfone (DDS) was used as the curing agent. The thermal and mechanical properties, fracture toughness, and morphology of the blends were investigated. Morphological analysis of the blends revealed a particulate structure with PEEKTOH phase dispersed in the epoxy matrix. Unlike classical polymer blend systems, increase in concentration of PEEKTOH does not increase the domain size. Instead, a decrease is obtained. The fracture toughness increased with the addition of oligomer without much decrease in tensile and flexural strengths. Addition of 15 phr oligomer gave maximum toughness. The dispersed PEEKTOH initiated several mechanisms that improved the fracture toughness of the blends. The cross‐link density calculated from the storage modulus in the rubbery plateau region decreased with the increase in PEEKTOH. The thermal stability of epoxy resin remained unaffected even after blending with PEEKTOH. POLYM. ENG. SCI., 45:1645–1654, 2005. © 2005 Society of Plastics Engineers