Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–vinyl ester oligomer–modified unsaturated polyester interpenetrating matrices for advanced composites

Interpenetrating networks of varying percentages of bismaleimide (BMI) in vinyl ester oligomer (VEO) modified unsaturated polyester (UP) matrices have been developed. Vinyl ester oligomer was prepared by reacting commercially available epoxy resin GY 250 (Ciba‐Geigy) and acrylic acid, and used as a toughening agent for unsaturated polyester resin. Unsaturated polyesters modified with 10, 20, and 30 wt % vinyl ester oligomer were made. The VEO toughened unsaturated polyester matrix systems, further modified with 5, 10, and 15 wt % bismaleimide (BMI). BMI–VEO–UP matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties according to ASTM methods: tensile strength, flexural strength, and unnotched Izod impact test. Data obtained from mechanical studies and thermal characterization indicate that the introduction of VEO and BMI into unsaturated polyester resin improves thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2502–2508, 2002     

Preparation and characterization of siliconized epoxy/bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane) intercrosslinked matrices for engineering applications

Novel hybrid intercrosslinked networks of hydroxyl‐terminated polydimethylsiloxane‐modified epoxy and bismaleimide matrix systems have been developed. Epoxy systems modified with 5, 10, and 15 wt % of hydroxyl‐terminated polydimethylsiloxane (HTPDMS) were developed by using epoxy resin and hydroxyl‐terminated polydimethylsiloxane with γ‐aminopropyltriethoxysilane (γ‐APS) as compatibilizer and dibutyltindilaurate as catalyst. The reaction between hydroxyl‐terminated polydimethylsiloxane and epoxy resin was confirmed by IR spectral studies. The siliconized epoxy systems were further modified with 5, 10, and 15 wt % of bismaleimide (BMI). The matrices, in the form of castings, were characterized for their mechanical properties. Differential scanning calorimetry and thermogravimetric analysis of the matrix samples were also performed to determine the glass‐transition temperature and thermal‐degradation temperature of the systems. Data obtained from mechanical studies and thermal characterization indicate that the introduction of siloxane into epoxy improves the toughness and thermal stability of epoxy resin with reduction in strength and modulus values. Similarly the incorporation of bismaleimde into epoxy resin improved both tensile strength and thermal behavior of epoxy resin. However, the introduction of siloxane and bismaleimide into epoxy enhances both the mechanical and thermal properties according to their percentage content. Among the siliconized epoxy/bismaleimide intercrosslinked matrices, the epoxy matrix having 5% siloxane and 15% bismaleimide exhibited better mechanical and thermal properties than did matrices having other combinations. The resulting siliconized (5%) epoxy bismaleimide (15%) matrix can be used in the place of unmodified epoxy for the fabrication of aerospace and engineering composite components for better performance. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 38–46, 2001     

Synthesis,characterization, and properties of low viscosity tetra‐functional epoxy resin N,N,N′,N′‐ tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane

Tetra‐functional epoxy resin N,N,N′,N′‐tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane (TGDEDDM) was synthesized and characterized. The viscosity of TGDEDDM at 25°C was 7.2 Pa·s, much lower than that of N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM). DSC analysis revealed that the reactivity of TGDEDDM with curing agent 4,4′‐diamino diphenylsulfone (DDS) was significantly lower than that of TGDDM. Owing to its lower viscosity and reactivity, TGDEDDM/DDS exhibited a much wider processing temperature window compared to TGDDM/DDS. Trifluoroborane ethylamine complex (BF₃‐MEA) was used to promote the curing of TGDEDDM/DDS to achieve a full cure, and the thermal and mechanical properties of the cured TGDEDDM were investigated and compared with those of the cured TGDDM. It transpired that, due to the introduction of ethyl groups, the heat resistance and flexural strength were reduced, while the modulus was enhanced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40009.     

Preparation and characterization of 3,3′‐bis (maleimidophenyl)phenylphosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices

An intercrosslinked network of polysulfone (PSF)—bismaleimide (BMI) modified epoxy matrix system was made by using diglycidyl ether of bisphenol A (DGEBA) epoxy resin, hydroxyl terminated polysulfone and bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide) with diaminodiphenylmethane (DDM) as curing agent. BMI–PSF–epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, flexural strength, and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of polysulfone into epoxy resin improves the toughness to an appreciable extent with insignificant increase in stress–strain properties. DSC studies indicated that the introduction of polysulfone decreases the glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of polysulfone as well as BMI modified epoxy resin show a unimodal reaction exotherm. The thermal stability and flame retardant properties of cured epoxy resins were improved with the introduction of bismaleimide and polysulfone. Water absorption characteristics were studied as per ASTM method and the morphology of the BMI modified epoxy and PSF‐epoxy systems were studied by scanning electron microscope. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Preparation and characterization of chain‐extended bismaleimide modified polyurethane–epoxy matrices

Intercrosslinked networks of bismaleimide (BMI) modified polyurethane–epoxy systems were prepared from chain‐extended BMI and polyurethane modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the grafting of polyurethane onto the epoxy skeleton. The prepared matrices were characterized by mechanical, thermal, and morphological studies. The results, obtained from the mechanical and thermal studies, reveal that the incorporation of polyurethane into epoxy increases the mechanical strength and decreases the glass‐transition temperature and thermal stability. The incorporation of chain‐extended BMI into polyurethane modified epoxy systems increases the thermal stability and both tensile and flexural properties, and decreases the impact strength and glass‐transition temperature. Surface morphologies of polyurethane modified epoxy and chain‐extended BMI modified polyurethane– epoxy systems were studied by scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1562–1568, 2003     

4,4′‐Bismaleimidodiphenyl methane modified novolak resin/titania nanocomposites: Preparation and properties

4,4′‐Bismaleimidodiphenyl methane modified novolak resin/titania nanocomposites were prepared by the sol–gel process of tetrabutyl titanate in the presence of 4,4′‐bismaleimidodiphenyl methane modified novolak resin prepolymers with acetyl acetone as a stabilizer. These nanocomposite materials were characterized by Fourier transform infrared analysis, dynamical mechanical analysis, thermogravimetric analysis, transmission electron microscopy, and field emission scanning electron microscopy. Nanometer titania particles were formed in the novolak resin matrix, and the average original particle size of the dispersed phase in the nanocomposites was less than 150 nm, but particle aggregates of larger size existed. The introduction of the titania inorganic phase with a nanoscale domain size did not improve the glass‐transition temperature of the nanocomposites but lowered the thermal resistance of the material because of the incomplete removal of acetyl acetone coordinated with tetrabutyl titanate, and it improved the modulus of the material at lower temperatures (<200°C) but lowered the modulus at higher temperatures (>250°C). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 52–57, 2006     

Thermal behavior and cured products of bis(4‐maleimidodiphenyl)methane,bis(isomaleimidodiphenyl)methane and 4,4′‐diaminodiphenyl methane mixtures

The thermal behavior of mixtures of bis(4‐maleimidophenyl) (A) with bis(4‐isomaleimidophenyl)methane (C) and their mixture with 4,4′‐diaminodiphenyl methane (D) were investigated by differential scanning calorimetry. The study of the binary system A/C in different proportions led us to determine an eutectic mixture at a molar fraction of C in the range of 0.7–0.9. The ternary ACD mixtures showed themselves able to participate in three principal reactions: polyaddition, ring‐opening addition, and homopolymerization. In each mixture studied the addition of diamine changed the melting point and maximum polymerization temperatures in the sense of a general decrease. The properties of the networks were studied by thermal analysis and through evaluation of water absorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3547–3556, 2003     

Peroxide crosslinking of a styrene‐free unsaturated polyester

Thermoset unsaturated polyesters are usually obtained by the crosslinking of unsaturated polyester chains dissolved in an unsaturated, reactive, monomeric diluent, which is usually styrene. This article describes a new approach in which styrene‐free unsaturated polyester chains are intrinsically cured into a crosslinked matrix. The gel time, gel content, swelling degree, glass‐transition temperature, dynamic mechanical properties, tensile properties, and molecular weight between crosslinks (calculated according to both the Flory–Rehner equation and the theory of rubber elasticity) of the crosslinked polymer are studied as a function of the peroxide concentration. All properties change considerably upon the addition of small amounts of peroxide (between 1 and 2 wt %) and change to a lesser extent with higher peroxide concentrations (up to 6 wt %). The thermal properties of the isolated gel fraction are studied as a function of the peroxide concentration. The sol fraction demonstrates a plasticizing effect on the crosslinked network, affecting the glass‐transition temperature and stress–strain behavior of the crosslinked polymer. In light of the crosslink densities derived from swelling experiments, a molecular structure and crosslinking mechanism are suggested for the gel fractions of 1 and 6 wt % peroxide crosslinked unsaturated polyester chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of novel poly[cyclotriphosphazene‐co‐(4,4′‐sulfonyldiphenol)] nanofiber matrices

Novel poly[cyclotriphosphazene‐co‐(4,4′‐sulfonyldiphenol)] nanofiber matrices were synthesized via a facile one‐pot polymerization. The fibers are 20–50 nm in diameter and 500 nm or more in length. Uniform nanoscale fibers linked covalently with each other and formed three‐dimensional matrices. The highly cross‐linked chemical structure of the nanofiber matrices was measured by means of Fourier transform infrared and quantitative solid‐state NMR spectroscopy. Experiments show the pH had an effect on the hydrolytic degradation of the polymer. The hydrolysis of the matrices could be accelerated by alkaline conditions. The as‐synthesized nanofiber matrices have potential applications in tissue engineering materials. Copyright © 2006 Society of Chemical Industry     

4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane: Synthesis and characterization

The paper describes the successful synthesis of silicon containing bismaleimide resin 4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane. The char yield of the bismaleimide resin in N₂ atmosphere was found to be 55% at 800°C. Chain extension of bismaleimide with 4,4′-diamino diphenyl sulfone reduced the char yield and thermal stability.     

Synthesis and characterization of aromatic polyesters and copolyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol and 4,4′‐(9‐fluorenylidene)diphenol

Two isophthalic polyesters from 4,4′‐(1‐hydroxyphenylidene)diphenol (BAP/ISO) and 4,4′‐(9‐fluorenylidene)diphenol (BF/ISO), and three different copolyesters containing 75, 50, and 25 mol % of BAP/ISO were synthesized by interfacial polycondensation. This preparation method yielded polymers and copolymers that produced flexible and transparent films when they were cast from solution. Proton NMR spectrometry studies showed that the isophthalic copolyesters were obtained as random copolymers with differences in comonomer composition no larger than 2.5 mol % with respect to the expected compositions. Wide‐angle X‐ray diffraction measurements indicated that all the polyesters and copolyesters were amorphous. The copolyesters showed amorphous patterns with maxima that fell between those of the polyesters. It was also found that thermal properties such as glass‐transition temperature, onset of decomposition temperature, thermal stability, dynamic mechanical storage modulus, and maximum on the α‐transition of the damping factor tan δ of BF/ISO were higher than those of BAP/ISO. The values of these thermal properties in the copolyesters fell between those of the polyesters and were dependent on the amounts of BF/ISO and BAP/ISO present in the copolyester in a linear fashion. Therefore, the thermal properties of a given copolyester can be predicted directly from the comonomers' composition. Overall, it shows that the interfacial polycondensation method is suitable to obtain these copolyesters in a controlled manner and that their properties can be tailored to be between those of the homopolyesters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2515–2522, 2002     

Preparation and porous structure characterization of 4,4′‐diphenylmethane dimethacrylate/divinylbenzene polymeric particles

Copolymers of isobutyl 4,4′‐diphenylmethane dimethacrylate and divinylbenzene in the form of microspheres were obtained. For their preparation, the following techniques of heterogeneous polymerization were used: suspension polymerization, suspension–emulsion polymerization, and precipitation polymerization. Among the obtained microspheres, those synthesized by suspenson–emulsion polymerization were of a size suitable for high‐performance liquid chromatography, whereas the product of suspension polymerization could be used as a packing material for gas chromatography. Their porous structure was studied in details. The influence of the polymerization technique on the particle size and morphology was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 863–870, 2005     

Replacement of styrene with acrylated epoxidized soybean oil in an unsaturated polyester resin from propylene glycol,isophthalic acid,and maleic anhydride

Commercial unsaturated polyester (UPE) resins typically contain a high amount of volatile toxic styrene. A non‐volatile acrylated epoxidized soybean oil (AESO) was found to be an excellent replacement of styrene in a commercially available UPE resin [designated as Styrene‐(PG‐IPA‐MA)] that is derived from propylene glycol (PG), isophthalic acid (IPA), and maleic anhydride (MA) in terms of the mechanical properties of the resulting kenaf fiber‐reinforced composites. The AESO‐(PG‐IPA‐MA) resins had low viscosity and long pot life below 70°C for a typical fiber‐reinforced composite application. AESO and PG‐IPA‐MA were not able to form a strong polymer matrix individually for fiber‐reinforced composites. However, a combination of AESO and PG‐IPA‐MA saw strong synergistic effects between them. The flexural, tensile, and water absorption properties of kenaf fiber‐reinforced composites made from AESO‐(PG‐IPA‐MA) resins were comparable with or even superior to those from the Styrene‐(PG‐IPA‐MA) resin. The AESO/(PG‐IPA‐MA) weight ratio was investigated for maximizing the mechanical properties of the kenaf fiber‐reinforced composites. The curing mechanism of the AESO‐(PG‐IPA‐MA) resins is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43052.     

Silica nanoparticles modified with vinyltriethoxysilane and their copolymerization with N,N′‐bismaleimide‐4,4′‐diphenylmethane

The synthesis and characterization of the vinyltriethoxysilane‐modified silica nanoparticles were investigated. It was shown that the vinyltriethoxysilane molecules had been successfully grafted onto the silica nanoparticles. The native and silane‐modified silica dispersions in N‐methyl‐2‐pyrrolidone with the total solids contents within the range 1–6 wt % exhibited dramatically different flow behaviors. The polymerization of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) initiated by barbituric acid in the presence of the native or vinyltriethoxysilane‐modified silica nanoparticles were then carried out in γ‐butyrolactone (total solids content = 20%). The higher the level of silica, the better the thermal stability of the BMI/silane/silica composite particles. The silane‐modified silica particles significantly improved their dispersion capability within the continuous BMI oligomer matrix. Furthermore, the degree of dispersion of the vinyltriethoxysilane‐modified silica particles in the BMI oligomer matrix decreased with the weight percentage of silica based on total solids increased from 20 to 40 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: Sci 103: 3600–3608, 2007     

Ambipolar and multi‐electrochromic polyimides based on N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline

A series of novel aromatic polyimides were synthesized from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic tetracarboxylic dianhydrides through a conventional two‐step procedure. Most of the polyimides exhibited reasonable solubility in organic solvents and could afford robust films via solution casting. The polyimides exhibited high thermal stability, with glass transition temperatures in the range 227–273 °C and 10% weight‐loss temperatures in excess of 550 °C. All the polyimide films showed ambipolar redox and multi‐electrochromic behaviors. They exhibited two reversible oxidation redox couples at 0.94–0.98 and 1.09–1.12 V versus Ag/AgCl in acetonitrile solution. A coupling reaction between the radical cations of the pendent triphenylamine units occurred during the oxidative process forming a tetraphenylbenzidine structure which resulted in an additional redox state and color change. © 2014 Society of Chemical Industry     

Curing kinetics and thermal property characterization of an o‐cresol formaldehyde epoxy resin and 4,4′‐diaminodiphenyl ether system

The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol^?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004     

Preparation and properties of high performance phthalide‐containing bismaleimide modified epoxy matrices

A series of intercrosslinked networks formed by diglycidyl ether of bisphenol A epoxy resin (DGEBA) and novel bismaleimide containing phthalide cardo structure (BMIPP), with 4,4′‐diamino diphenyl sulfone (DDS) as hardener, have been investigated in detail. The curing behavior, thermal, mechanical and physical properties and compatibility of the blends were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), notched Izod impact test, scanning electron microscopy (SEM) and water absorption test. DSC investigations showed that the exothermic transition temperature (T_p) of the blend systems shifted slightly to the higher temperature with increasing BMIPP content and there appeared a shoulder on the high‐temperature side of the exothermic peak when BMIPP content was above 15 wt %. TGA and DMA results indicated that the introduction of BMIPP into epoxy resin improved the thermal stability and the storage modulus (G′) in the glassy region while glass transition temperature (T_g) decreased. Compared with the unmodified epoxy resin, there was a moderate increase in the fracture toughness for modified resins and the blend containing 5 wt % of BMIPP had the maximum of impact strength. SEM suggested the formation of homogeneous networks and rougher fracture surface with an increase in BMIPP content. In addition, the equilibrium water uptake of the modified resins was reduced as BMIPP content increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of unsaturated polyester and alkyd resins using one‐ and two‐dimensional NMR spectroscopy

One‐ (1D) and two‐dimensional (2D) ¹H‐ and ¹³C‐NMR spectroscopy was used to characterize polyester and alkyd resins used in the coatings industry. The wealth of chemical composition information of the ¹H‐ and ¹³C‐NMR 1D spectra of the resins is revealed through 2D NMR experiments that spread chemical shifts in two dimensions, thus facilitating the peak assignment of the various components of the resins. It is shown that the types of polyols, acids, and vegetable oils used to modify the resins can be efficiently traced by NMR spectroscopic techniques. Information on the quantitative composition of the resins and especially the abundance of unsaturated fatty acid double bonds, which influences resin dryability and hardness, can be easily extracted from the ¹H‐NMR spectra upon successful assignment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1881–1888, 2003     

Properties of crosslinked polyurethanes synthesized from 4,4′‐diphenylmethane diisocyanate and polyester polyol

Polyurethanes were synthesized using the high functional 4,4′‐diphenylmethane diisocyanate (MDI), polyester polyol, and 1,4‐butane diol. The synthesized polyurethanes were analyzed using differential scanning calorimeter (DSC), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR) spectrometer, and swelling measurement using N,N′‐dimethylformamide. From the result of thermal analysis by DSC and DMTA, single T_gs were observed in the polyurethane samples at all the formulated compositions. From this result, it is suggested that the polyurethanes synthesized in this study have crosslinked structure rather than the phase‐separated segmented structure because of the high functionality (f = 2.9) of the MDI. By annealing the polyurethane samples using DSC, the T_gs were increased by 4.7∼16.0°C at the various annealing temperatures. From the results of FTIR and swelling measurement of polyurethanes, it is suggested that the increase of T_g of the polyurethanes by annealing is not due to increase of the hydrogen bond strength but mainly due to the increase of the crosslink density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 624–630, 2000     

Fracture and adhesion behaviors of epoxy resins modified with poly(amine‐quinone)

An amine‐quinone monomer, i.e. 2,5‐bis(4,4′‐methylenedianiline)‐1,4‐benzoquinone (BB), was synthesized by the Michael addition of 4,4′‐diaminodiphenyl methane with 1,4‐benzoquinone. To evaluate the effect of BB content on the glass transition temperature (T_g) and crosslinking density (ρ) of cured diglycidyl ether of bisphenol A (DGEBA)/BB systems, storage modulus and loss factor measurements were obtained using dynamic mechanical analysis. The mechanical properties of the systems were determined in terms of the fracture toughness, impact strength, and adhesion strength. As a result, the ρ values of the systems were found to decrease systematically as the BB content increased. The fracture toughness and adhesion strength of the systems increased with increasing BB content. These results indicate that the addition of BB into epoxy resins increases the free volume of the epoxy network and absorbs the deformation energy, resulting in an improvement of the mechanical properties of the DGEBA/BB systems. Copyright © 2006 Society of Chemical Industry