Preparation and characterization of siliconized epoxy‐1,2‐bis(maleimido)ethane intercrosslinked matrix materials

Novel intercrosslinked networks of siliconized epoxy‐1,2‐bis(maleimido)ethane matrix systems are developed. The siliconization of epoxy resin is carried out by using 5–15% hydroxyl‐terminated poly(dimethylsiloxane) with γ‐aminopropyltriethoxysilane as a crosslinking agent and dibutyltin dilaurate as a catalyst. The siliconized epoxy systems are further modified with 5–15% 1,2‐bis(maleimido)ethane and cured by using diaminodiphenylmethane. The prepared neat resin castings are characterized for their mechanical properties. Mechanical studies indicate that the introduction of siloxane into these epoxy resins improves the toughness with a reduction in the stress–strain values, whereas incorporation of bismaleimide (BMI) into the epoxy resin improves the stress–strain properties with a lowering of the toughness. The introduction of both siloxane and BMI into the epoxy resin influences the mechanical properties according to their content percentages. Differential scanning calorimetry (DSC), thermogravimetry, and heat distortion temperature analyses are also carried out to assess the thermal behavior of the matrix materials that are developed. DSC thermograms of the BMI modified epoxy systems show unimodal reaction exotherms. The glass‐transition temperature, thermal degradation temperature, and heat distortion temperature of the cured BMI modified epoxy and siliconized epoxy systems increase with increasing BMI content. The water absorption behavior of the matrix materials is also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3808–3817, 2003     

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     

Studies on thermal and morphological behavior of siliconized epoxy bismaleimide matrices

Novel bismaleimide‐modified siliconized epoxy intercrosslinked network systems were developed. Siliconized epoxy systems containing 5, 10, and 15% siloxane units were prepared using epoxy resin and hydroxyl‐terminated polydimethylsiloxane (HTPDMS) with γ‐aminopropyltriethoxysilane (γ‐APS) as a compatibilizer and dibutyltindilaurate as a catalyst. The siliconized epoxy systems were further modified with 5, 10, and 15% (wt %) of bismaleimide [(N,N′‐bismaleimido‐4,4′‐diphenylmethane) (BMI)] and cured by diaminodiphenylmethane (DDM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat‐distortion temperature measurement of the matrix samples were carried out to assess their thermal behavior. DSC thermograms of the BMI‐modified epoxy systems show unimodel reaction exotherms. The glass transition temperature (T_g) of the cured BMI‐modified epoxy and siliconized epoxy systems increases with increasing BMI content. Thermogravimetric analysis and heat‐distortion temperature measurements indicate that the thermal degradation temperature and heat‐distortion temperature of the BMI‐modified epoxy and siliconized epoxy systems increase with increasing BMI content. The morphology of the BMI‐modified siliconized epoxy systems was also studied by scanning electron microscopy (SEM). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2330–2346, 2001     

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     

Development and characterization of phosphorus-containing siliconized epoxy resin coatings

The objective of the present work is the development and characterization of siliconized epoxy-phosphorus based bismaleimide coating systems using diglycidylether terminated poly (dimethylsiloxane) (DGTPDMS) and phosphorus-containing bismaleimide (PBMI) as chemical modifiers for epoxy resin. Phosphorus-containing diamine (DOPO-NH₂) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 4,4′-diaminobenzophenone (DABP), which was utilized in the preparation of phosphorus-containing bismaleimide (PBMI) with maleic anhydride. Siliconized epoxy prepolymer was prepared using epoxy resin and functionally terminated polydimethylsiloxane. The purity and structural conformation of these materials were ascertained from FTIR and NMR spectral studies. The prepared siliconized epoxy prepolymer was blended with varying percentages of PBMI using diaminodiphenylsulfone (DDS) and diaminodiphenylmethane (DDM) as curing agents. The siliconized epoxy and bismaleimide modified epoxy and siliconized epoxy coating materials were characterized by dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), heat distortion temperature (HDT) and Limiting oxygen index (LOI).     

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     

Mechanical and morphological properties of organic–inorganic,hybrid, clay‐filled,and cyanate ester/siloxane toughened epoxy nanocomposites

Organic–inorganic hybrids involving cyanate ester and hydroxyl‐terminated polydimethylsiloxane (HTPDMS) modified diglycidyl ether of bisphenol A (DGEBA; epoxy resin) filled with organomodified clay [montmorillonite (MMT)] nanocomposites were prepared via in situ polymerization and compared with unfilled‐clay macrocomposites. The epoxy‐organomodified MMT clay nanocomposites were prepared by the homogeneous dispersion of various percentages (1–5%), and the resulting homogeneous epoxy/clay hybrids were modified with 10% HTPDMS and γ‐aminopropyltriethoxysilane as a coupling agent in the presence of a tin catalyst. The siliconized epoxy/clay prepolymer was further modified separately with 10% of three different types of cyanate esters, namely, 4,4′‐dicyanato‐2,2′‐diphenylpropane, 1,1′‐bis(3‐methyl‐4‐cyanatophenyl) cyclohexane, and 1,3‐dicyanato benzene, and cured with diaminodiphenylmethane as a curing agent. The reactions during the curing process between the epoxy, siloxane, and cyanate were confirmed by Fourier transform infrared analysis. The results of dynamic mechanical analysis showed that the glass‐transition temperatures of the clay‐filled hybrid epoxy systems were lower than that of neat epoxy. The data obtained from mechanical studies implied that there was a significant improvement in the strength and modulus by the nanoscale reinforcement of organomodified MMT clay with the matrix resin. The morphologies of the siloxane‐containing, hybrid epoxy/clay systems showed heterogeneous character due to the partial incompatibility of HTPDMS. The exfoliation of the organoclay was ascertained from X‐ray diffraction patterns. The increase in the percentage of organomodified MMT clay up to 5 wt % led to a significant improvement in the mechanical properties and an insignificant decrease in the glass‐transition temperature versus the unfilled‐clay systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical and Morphological Behavior of Bismaleimide-Modified Soy-Based Epoxy Matrices

This study is concerned with the preparation and mechanical characterization of bio-based polymers from renewable resources. Epoxidized soybean oil at various concentrations is cured with an amine curing agent. The prepared matrices have been chemically modified with three types of bismaleimides, namely N, N′-bismaleimido-4, 4′-diphenyl methane (BMI-1), 1,3-bis(maleimido)benzene(BMI-2) and 3,3′-bis(maleimido phenyl)phenyl phosphineoxide (BMI-3). The crosslinked matrices thus developed were characterized for their mechanical properties such as tensile strength, tensile modulus, flexural strength, flexural modulus, and impact strength. The incorporation of bismaleimides in the soy-based matrices significantly enhances the mechanical properties. The morphological behavior of matrices is also studied using a scanning electron microscope. The results indicate that the bismaleimide-modified soy-based epoxy resin at appropriate concentration holds great potential as a replacement for petroleum-based materials in engineering applications.     

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     

低温固化烯丙基酚氧树脂／双马来酰亚胺树脂的研究

为降低双马来酰亚胺树脂的固化温度,用2-甲基咪唑（2-MI）为烯丙基酚氧树脂／双马来酰亚胺树脂体系的固化催化剂,测试了改性树脂体系的凝胶化时间、力学性能和热性能,并探讨了催化剂含量对树脂性能的影响。结果表明,当催化剂质量分数为05％时,体系性能最佳。冲击强度为26．39kJ／m2,弯曲强度为14485MPa,热变形温度为202℃,树脂具有良好的韧性,并保持了优异的耐热性。     

环氧树脂改性双马来酰亚胺/氰酸酯树脂固化工艺研究

采用差示扫描量热(DSC)法和红外光谱(FT-IR)法对缩水甘油胺型环氧树脂(AG-80)与脂环族缩水甘油酯型环氧树脂(TDE-85)共同改性双马来酰亚胺(BMI)/氰酸酯树脂(CE)的固化反应历程进行了研究,并按照Kissinger和Crane法计算出该改性树脂体系固化反应的动力学参数。结果表明:改性树脂体系的固化反应表观活化能为68.11 kJ/mol,固化反应级数为0.860(接近于1级反应);环氧树脂(EP)可促进CE固化,当固化工艺条件为"150℃/3 h→180℃/2 h"时,改性树脂体系可以固化完全。     

BMI改性酚醛树脂模塑料的制备与性能研究

采用一步法合成了BMI(双马来酰亚胺)改性PF(酚醛树脂),通过FT-IR(红外光谱)法、1H-NMR(核磁共振氢谱)法、凝胶时间和DSC(差示扫描量热)法等分析了改性树脂的结构和固化温度,并分别以HMTA(六次甲基四胺)和PO(过氧化物)作为固化剂对不同BMI含量的改性PF模塑料进行了性能对比。结果表明:BMI改性PF在较高温度时才能固化,固化剂种类和BMI含量对改性PF模塑料的性能影响较大;以PO作为固化剂和引发剂时,相应模塑料的综合性能相对更好。     

Mechanical properties of E‐glass fiber reinforced siliconized epoxy polymer composites

Siliconized epoxy‐matrix systems have been developed by an interpenetrating mechanism using epoxy resins GY 250 and LY 556 (Ciba‐Geigy) and hydroxyl terminated polydimethylsiloxane with γ‐aminopropyltriethoxysilane as crosslinker in the presence of dibutyltindilaurate catalyst. Aliphatic amine (HY 951, Ciba‐Geigy), aromatic amine (HT 972, Ciba‐Geigy) and polyamidoamine (HY 840, Ciba‐Geigy) are used as curing agents for epoxy resins. The tentative level of 10% siloxane introduction into epoxy resin has been ascertained from experimental studies to obtain reasonable improvements in the impact behavior without compromising other mechanical properties. The impact behavior of E‐glass reinforced composites made from the siliconized epoxy resin is enhanced to 2–4 times over that measured on the composites made from a pure epoxy resin. Composites cured with aromatic amine impart better mechanical properties than those cured with aliphatic amine and polyamidoamine.     

Cure behavior and properties of an epoxy resin modified with a bismaleimide resin

A bismaleimide (BMI) resin was added to an epoxy system composed of N,N′-tetraglycidyldiaminodiphenyl methane (TGDDM) and diaminodiphenyl methane (DDM). Cure behavior of the BMI modified epoxy resins was studied by a dynamic differential scanning calorimetry (DSC) method. Dynamic DSC thermograms of the BMI modified epoxy resins indicated unimodal reaction exothermic peaks. The overall heat of reaction per unit mass decreased with BMI composition. The residual heat of reactions of the epoxy blends cured at 180°C for 3 h increased with BMI composition. Thermal stability of the epoxy system improved by incorporating BMI resin. Flexural strength and modulus increased with BMI composition.     

Mechanical Properties of Bismaleimides Modified Polysulfone Epoxy Matrices

Epoxy resin has been chemically modified using 4, 8, and 12% of bisphenol-A based polysulphone along with three types of bismaleimides, namely [N, N′-bismaleimido-4,4′-diphenylmethane (BMI-1), 1,3-bis (maleimido) benzene (BMI-2) and 1,1′-bis (4-maleimidophenyl) cyclohexane (BMI-3)]. The epoxy hybrid matrices developed, in the form of castings, were used to characterize their mechanical properties like tensile strength, tensile modulus, flexural strength, flexural modulus, impact strength, hardness, and dynamic mechanical analysis as per ASTM standards. Data obtained from mechanical studies indicate that the introduction of hydroxyl terminated polysulfone into epoxy resin enhanced the value of impact strength to the extent of 48% due to the formation of flexible graft structures. Similarly, the incorporation of bismaleimides into epoxy resin also improved both tensile and flexural behavior of epoxy resin. Further, the introduction of combination of both polysulfone and bismaleimides into epoxy resin improved the mechanical properties according to their percentage content. Among the bismaleimides-modified polysulfone epoxy matrices, the epoxy matrix modified with 8% polysulfone and 8% BMI-2 exhibited better mechanical properties than other modified epoxy matrices.     

Studies on mechanical,thermal, and morphology of diglycidylether‐terminated polydimethylsiloxane‐modified epoxy–bismaleimide matrices

An epoxy matrix system modified by diglycidylether‐terminated polydimethylsiloxane (DGETPDMS) and bismaleimide (BMI) was developed. Epoxy systems modified with 4, 8, and 12% (by wt) of DGETPDMS were made using epoxy resin and DGETPDMS, with diaminodiphenylmethane as the curing agent. The DGETPDMS‐toughened epoxy systems were further modified with 4, 8, and 12% (by wt) of BMI, namely (N,N′‐bismaleimido‐4,4′‐diphenylmethane). DGETPDMS/BMI/epoxy 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, viz. tensile strength, flexural strength, and impact test, as per ASTM methods. Mechanical studies indicate that the introduction of DGETPDMS into epoxy resin improves the impact strength, with reduction in tensile strength, flexural strength, and glass transition temperature, whereas the incorporation of BMI into epoxy resin enhances the mechanical and thermal properties according to its percentage content. However, the introduction of both DGETPDMS and BMI enhances the values of thermomechanical properties according to their percentage content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 668–674, 2006     

Modification of epoxy resin by addition of bismaleimide and diallyl phthalate

Epoxy resins are a very versatile class of compounds. They have excellent mechanical properties and are easily processable; however, their major drawback is their brittleness. An attempt was made to improve the impact strength of the epoxy without decreasing its other properties. In the present study a commonly used epoxy resin, diglycidyl ether of Bisphenol‐A, was modified by the addition of bismaleimide (BMI) and diallyl phthalate (DAP) and was cured with diaminodiphenylmethane and benzoyl peroxide. The composition incorporating 5 phr BMI showed maximum heat deflection temperature (HDT) and flexural strength with impact properties remaining almost unaffected. Further addition of BMI reduced the HDT and flexural properties but increased the impact strength. For epoxy‐DAP systems the maximum HDT and flexural strength were observed on addition of 5 phr DAP. Further addition of DAP lead to a decrease in all properties except impact strength, which was observed to increase. Incorporation of both BMI and DAP, simultaneously, into the epoxy resin resulted in improvement in mechanical properties for most of the compositions. However, the HDT was found to be less than that for unmodified epoxy. POLYM. ENG. SCI., 47:1881–1888, 2007. © 2007 Society of Plastics Engineers     

Study on properties of low dielectric loss resin matrix

Allyl phenyl compounds, allyl epoxy resins, and epoxy acrylate resins are adapted to copolymerize with bismaleimide (BMI) resins and to modify mechanical properties and processing properties. Reaction activity, physical properties, mechanical properties, dielectric properties, and thermal stability were investigated. Impact strength and flexural strength of modified BMI resin are increased about twice and 42% than that of pure BMI resin, respectively. Fracture elongation is from 1.6 to 2.3%. The fracture surfaces of the broken specimens are examined by scanning electron microscopy (SEM). As a result, modified BMI resins put up typical toughness rupture. The modified BMI resins possess excellent dielectric properties, and dielectric constant and dielectric loss almost hold the line with increasing epoxy concentration. When the test frequency scope is from 1 to 20 GHz, the dielectric constant and dielectric loss of modified BMI resins is 3.05–3.12 and 0.0089–0.012, respectively. The modified BMI resins still possess fine properties after hydrothermal aging. After 100 h in boiling water, the reservation ratios of both the impact strength and flexural strength of modified system exceeded 90%, and the water absorption and heat distortion temperature (HDT) is 2.6% and 235°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 315–319, 2006     

Toughened polyester matrices for advanced composites

An intercrosslinked network of hybrid bismaleimide (BMI) modified vinyl ester oligomer–unsaturated polyester matrix systems have been developed. Vinyl ester oligomer (VEO) was used as a toughening agent for unsaturated polyester resin and was added in 2, 4, and 6% (by wt). Benzoyl peroxide was used as curing agent. The VEO‐toughened unsaturated polyester matrix systems were further modified with 5, 10, and 15% (by wt) of bismaleimide. Bismaleimides modified vinyl ester–unsaturated polyester matrices were characterized by mechanical (tensile strength, flexural strength, tensile modulus, flexural modulus, and impact strength), thermal [differential scanning calorimetry (DSC), thermogravimetic analysis (TGA), heat deflection temperature analysis (HDT)] and morphological studies [scanning electron microscope (SEM)] and water absorption. Data obtained from mechanical studies indicated that the introduction of VEO into unsaturated polyester resin improves the fracture toughness. The introduction of BMI into VEO incorporated unsaturated polyester resin enhanced both thermal and mechanical behavior. The scanning electron micrographs of fractured surfaces of VEO‐modified unsaturated polyester systems and BMI modified vinyl ester–unsaturated polyester matrices illustrate the presence of homogeneous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 167–177, 2007     

改性BMI耐热树脂及其性能研究

用二苯甲烷双马来酰亚胺（BMI）和二烯丙基双酚A为主原料，辅以少量扩链剂A（体系Ⅰ）和再配加少量环氧树脂（ER）（体系Ⅱ），在混合溶剂中经热预聚制成了工艺性、粘接性和复盖性好、长期均相稳定，便于浸渍、涂敷和粘接的改性BMI胶液，测试了固化前后的性能，此改性增韧树脂的耐热和耐老化性与未改性BMI树脂相当，可在200℃长期使用。