Preparation and properties of cyanate ester/polyorganosiloxane blends with lower dielectric loss and improved toughness

Novel modified cyanate ester resins (EPMPS‐n/BADCy), with significantly decreased dielectric loss and improved toughness, were developed by copolymerizing the cyanate ester resin, 2, 2′‐bis (4‐cyanatophenyl) isopropylidene resin) (BADCy), with an epoxidized methyl phenyl silicone resin (EPMPS). The curing behavior of EPMPS‐n/BADCy and the typical properties of the corresponding cured EPMPS‐n/BADCy were systematically investigated. The results show that the addition of EPMPS into BADCy can not only accelerate the curing reaction of BADCy, but also decrease dielectric loss and enhance the impact strength as well as water resistance. For example, in the case of the modified BADCy resin with 15 wt%EPMPS, its impact strength is 17.8 kJ/m², about 3 times of that of pure BADCy resin and its water absorption is only 0.25%, about one‐half of that of pure BADCy resin. In addition, while the dielectric loss is only 79% of that of pure BADCy resin, while its dielectric constant remains constant over the frequency range of 1KHz‐1 MHz. The above results suggest that EPMPS‐n/BADCy have great potential to be used as the matrix or adhesive for advanced composites. Copyright © 2009 John Wiley & Sons, Ltd.     

The thermal and dielectric properties of high performance cyanate ester resins/microcapsules composites

Novel high performance bisphenol A dicyanate ester (BADCy) resins/poly(urea-formaldehyde) microcapsules filled with epoxy resins (MCEs) composites have been prepared. The effects of different contents of MCEs on the thermal and dielectric properties of cured BADCy were investigated using dynamic mechanical analyzer (DMA), thermalgravimetric analyzer (TGA) and broadband dielectric analyzer. The dielectric properties of BADCy/MCEs treated in hot water and hot air were also discussed. The morphologies of BADCy/MCEs composites were characterized by scanning electron microscopy (SEM). Results indicate that the appropriate content of MCEs can improve or maintain the thermal stability, the low dielectric constant and dielectric loss of cured BADCy mainly owing to higher conversion of cyanate ester (-OCN) groups. After aged in hot water and hot air, respectively, BADCy/MCEs composites with small content of MCEs can retain the low dielectric constant and dielectric loss.     

High performance toughened cyanate ester resin with low injection temperature for RTM process

A high‐performance modified cyanate resin system with low injection temperature for fabricating advanced composites via resin transfer molding (RTM) was developed, which was made of bisphenol A dicyanate ester (BADCy) and diallyl phthalate (DAP). The processing characteristics, mechanical, and thermal properties of the resin were studied, and the effect of the content of DAP on the processing and performance parameters was discussed. The results show that the processing properties of the modified cyanate system are dependent on the content of DAP. All the formulations studied in this paper have good processing characteristics; their injection temperatures are between 30 and 40°C and the pot life is about 20 hr at 50°C. The cured resins exhibited good thermal stability, excellent toughness, and good hot–wet resistance, suggesting that the toughened cyanate resin is a potential high‐performance RTM matrix for advanced composites. Copyright © 2008 John Wiley & Sons, Ltd.     

聚苯乙炔基苯基硅氧硼烷树脂及其复合材料的性能

将双(N-间乙炔基苯基邻苯二甲酰亚胺)醚(DAIE)和双酚A型氰酸酯(CE)分别加到聚苯乙炔基苯基硅氧硼烷(PSOB)和三苯乙炔基苯基硅烷(PTPES)混合体系中进行改性,制得两种纤维增强复合材料PSOB-PTPES-DAIE和PSOB-PTPES-CE.研究了固化后树脂的热稳定性能、力学性能、介电性能和耐水性能.结果...     

Viscoelastic properties and morphology of dicyanate ester/epoxy co-polymers modified with polysiloxane and butadiene–acrylonitrile rubbers

Dynamic mechanical analysis was conducted on specimens prepared from cyanate ester (CE) and epoxy (EP) resins cured together at various mass compositions. Increase of amount of epoxy resin in composition was shown to have a disadvantageous effect on glass transition temperature (T _g). It was shown that post-curing procedure was needed to produce a polymer matrix with a single glass transition relaxation, but increase in post-cure temperature up to 250 °C resulted in slight reduction in T _g for epoxy/cyanate copolymers. TG results proved that the presence of epoxy resin reduces thermal stability of the cyanate/epoxy materials. The neat CE and EP/CE systems containing 30 wt% of epoxy resin were modified using epoxy-terminated butadiene–acrylonitrile rubber (ETBN) and polysiloxane core–shell elastomer (PS). The scanning electron microscopy (SEM) results showed the existence of second phase of ETBN and PS modifiers. Only in the case of EP/CE composition modified with ETBN, well-dispersed second phase domains were observed. Analysis of SEM images for other CE- and EP/CE-modified systems revealed the formation of spherical aggregates.     

Study on properties of flame‐retardant cyanate esters modified with DOPO and triazine compounds

Ternary flame‐retardant modified cyanate ester blends (CEPG and CEPA) are formed by combining triazine compounds (TGIC or TAIC) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide with cyanate ester resin. The curing behaviors, thermal and mechanical properties, and the flame‐retardant properties are investigated. The results show that the CEPG and CEPA blends result in lower curing temperatures and glass transition temperatures than those of neat CE. Both of CEPG and CEPA blends significantly improve the flame‐retardant properties of CE resins, and UL‐94V‐0 rate is achieved for CEPG‐1.0 and CEPA‐0.5. The dielectric constant and loss of CEPA blends are lower than those of CEPG blend with the same phosphors content, and both of them are lower than those of neat CE. Therefore, the ternary flame‐retardant modified cyanate ester blends provide 2 ways for composites of producing printed circuit board with high flame‐retardant property and low dielectric constant and loss.     

Three-phase cyanate ester composites with fumed silica and negative-CTE reinforcements

Three-phase cyanate ester adhesives have been developed using a bisphenol E cyanate ester resin, fumed silica, and negative-CTE (coefficient of thermal expansion) reinforcements: short carbon fiber or zirconium tungstate (ZrW₂O ₈ ). Fumed silica was used to impart thixotropic behavior on the resin and decrease settling in the adhesives. The cured composites were evaluated using various thermal analysis techniques for their thermal-mechanical properties. Composites with short carbon fiber showed enhanced modulus and decreased thermal expansion (70% reduction for 20 vol%) and showed little phase separation. While settling of the dense ceramic particles could not be completely eliminated for the zirconium tungstate composites through rheological modification of the adhesive with added fumed silica, a reduction in CTE of 84% was achieved in the composite (58 vol%) compared to the neat resin. In addition, the effect of thermal history on the cure and temperature induced ZrW₂O₈ phase transitions, and their corresponding influence on thermal strains vs. temperature, are examined by thermomechanical analysis.     

Novel toughened cyanate ester resin with good dielectric properties and thermal stability by copolymerizing with hyperbranched polysiloxane and epoxy resin

A novel toughened cyanate ester (CE) resin with good dielectric properties and thermal stability was developed by copolymerizing 2,2′‐bis(4‐cyanatophenyl)iso‐propylidene (BCE) with a combined modifier (HBPSiEP) made up of hyperbranched polysiloxane (HBPSi) and epoxy (EP) resin. HBPSi was synthesized through the hydrolysis of 3‐(trimethoxysilyl)propyl methacrylate. The effect of differing stoichiometries of HBPSiEP on the curing characteristics and performance of BCE resin is discussed. Results show that the incorporation of HBPSiEP can not only effectively promote the curing reaction of BCE, but can also significantly improve the toughness of the cured BCE resin. In addition, the toughening effect of HBPSiEP is greater than single EP resin. For example, the impact strength of modified BCE resin with 30 wt% of HBPSiEP is 23.3 KJ/m², which is more than 2.5 times of that of pure BCE resin, while the maximum impact strength of EP/BCE resin is about 2 times of pure BCE resin. It is worthy to note that HBPSiEP/BCE resins also exhibit improved thermal stability, dielectric properties, and flame retardancy, suggesting that the novel toughened CE resins have great potentiality to be used as a matrix for advanced functional composites or electronic packing resins. Copyright © 2009 John Wiley & Sons, Ltd.     

长链双马来酰亚胺改性氰酸酯树脂及其复合材料

制备了长链双马来酰亚胺改性的氰酸酯树脂及其复合材料, 并对其进行了表征. 结果表明, 当长链双马树脂(MTHMI)占改性树脂的质量分数为37.5%时, 改性树脂(MTI/T₃)的5%热失重温度为414℃, 复合材料在室温和200℃时的拉伸强度分别为431.2和331.0 MPa, 弯曲强度分别为631.5和278.4 MPa, 复合材料的X-Y轴热膨胀系数为18.1×10^-6℃^-1, 吸湿率为1.4%. 实验结果表明, 该类树脂与普通双马改性氰酸酯树脂及分别由质量分数为20%和30% MTHMI改性的氰酸酯树脂MTI/T₁和MTI/T₂相比, 具有良好的加工性, 优异的耐热性和力学性能, 较低的吸湿性和热膨胀系数.     

Cyanate Ester/Functionalized Silica Nanocomposite: Synthesis,Characterization and Properties

In this paper silica nanoparticles with covalently grafted polymer chains were incorporated into bisphenol A dicyanate ester (BADCy) to prepare composites which resulted in improvements in the mechanical and thermal properties. Fourier‐transform infrared (FT‐IR) spectroscopy transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were employed to examine the surface functionalization of silica nanoparticles. The effects of functionalized SiO₂ (F‐SiO₂) on the curing reactivity mechanical and thermal properties of BADCy resin were investigated systematically. The curing reaction of the system was facilitated with the addition of F‐SiO₂. Meanwhile compared with the neat resin the incorporation of appropriate content of modified F‐SiO₂ can enhance the mechanical properties including impact flexural strengths and fracture toughness K_IC of BADCy resin. In addition the thermal stability of BADCy/F‐SiO₂ nanocomposites is also superior to that of pure BADCy resin.     

Curing of dicyanate ester/epoxy copolymers modified with polysiloxane and butadiene-acrylonitrile rubbers

The cyanate ester (CE) and epoxy (EP) resins were cured together at various mass compositions. The curing behavior of CE and CE/EP systems was studied by means of differential scanning calorimetry (DSC) in non-isothermal conditions. The DSC measurements indicated that the curing reactions were dependent on the stoichiometric ratio of the mixtures and showed the dilution effect of the EP resin in the cyclotrimerization of the catalyzed CE resin. The CE and CE/EP (70/30) systems were modified using reactive liquid butadiene-acrylonitrile copolymer (ETBN) and polysiloxane core?Cshell (PS) elastomer. The influence of ETBN and PS on the curing process and glass transition temperature (T _g) of CE/EP systems was determined. The impact resistance characteristics of the completely cured systems indicated the influence of the modifiers and the EP content in the mixtures on its impact resistance.     

Thermal and mechanical evaluation of cyanate ester resin modified with bismaleimide and diallyl phthalate

Cyanate ester resins have excellent dielectric, mechanical, and thermal properties; however, their major drawback is their brittleness. A high performance matrix blend was developed using bisphenol A dicyanate (BADCy), bismaleimide (BMI) and diallyl phthalate (DAP), and Cobalt (III) acetylacetonate dissolved in nonyl phenol (NP) as a complex catalyst system for BADCy. The properties of the BADCy/BMI/DAP blends, such as thermal and mechanical properties, were investigated in detail by dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and mechanical measurement. The results show that the addition of the appropriate amount of DAP and BMI can improve the impact strength and the flexural strength and this possibly comes from forming an interpenetrating polymer network in the systems. However, the thermal stability of the blends was found to be lower than that of the unmodified BADCy resin. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on thermal and morphological properties of 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane-epoxy-bismaleimide matrices

A new cyanate ester monomer, 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane has been synthesized and characterized. Epoxy modified with 4, 8 and 12% (by weight) of cyanate ester were made using epoxy resin and 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane and cured by using diaminodiphenylmethane. The cyanate ester modified epoxy matrix systems were further modified with 4, 8 and 12% (by weight) of bismaleimide (N,N′-bismaleimido-4,4′-diphenylmethane). The formation of oxazolidinone and isocyanurate during cure reaction of epoxy and cyanate ester blend was confirmed by IR spectral studies. Bismaleimide-cyanate ester-epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. Thermal studies indicate that the introduction of cyanate ester into epoxy resin improves the thermal degradation studies at the expense of glass transition temperature. Whereas the incorporation of bismaleimide into epoxy resin enhances the thermal properties according to its percentage content. However, the introduction of both cyanate ester and bismaleimide influences the thermal properties according to their percentage content. DSC thermogram of cyanate ester modified epoxy and bismaleimide modified epoxy show unimodel reaction exotherms. The thermal degradation temperature and heat distortion temperature of the cured bismaleimide modified epoxy and cyanate ester-epoxy systems increased with increasing bismaleimide content. The morphology of the bismaleimide modified epoxy and cyanate ester-epoxy systems were also studied by scanning electron microscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

Modified cyanate ester resins with lower dielectric loss,improved thermal stability,and flame retardancy

Novel modified cyanate ester (CE) resins with decreased dielectric loss, improved thermal stability, and flame retardancy were developed by copolymerizing CE with hyperbranched phenyl polysiloxane (HBPPSi). HBPPSi was synthesized through the hydrolysis of phenyltrimethoxysilane, and its structure was characterized by ¹H‐NMR, ²⁹Si‐NMR, and Fourier transform infrared spectra. The effect of the incorporation of HBPPSi into CE resin on the curing behavior, chemical structure of cured networks, and typical performance of HBPPSi/CE resins were systemically evaluated. It is found that the incorporation of HBPPSi into CE network obviously not only catalyzes the curing of CE, but also changes the chemical structure of resultant networks, and thus results in significantly decreased dielectric loss, improved thermal stability, and flame retardancy as well as water absorption resistance. For example, in the case of the modified CE resin with 10 wt% HBPPSi, its limited oxygen index is about 36.0, about 1.3 times of that of neat CE resin, its char yield at 800°C increases from 31.6 to 35.4 wt%; in addition, its dielectric loss is only about 61% of that of neat CE resin at 1 kHz. All these changes of properties are discussed from the view of the structure–property relationship. The significantly improved integrated properties of CE resin provide a great potential to be used as structural and functional materials for many cutting‐edges fields. Copyright © 2011 John Wiley & Sons, Ltd.     

含磷有机硅杂化环氧树脂固化体系性能研究

通过磷酸与γ-环氧丙氧基三甲氧基硅烷反应得到含磷有机硅氧烷,并加入到环氧树脂/4,4'-二氨基二苯基甲烷体系中混合,通过溶胶-凝胶的方法制备了含磷有机硅杂化环氧树脂固化物.对固化体系进行了玻璃化转变温度、热失重、阻燃、拉伸强度、冲击强度测试分析.结果表明,该固化体系的阻燃性得到提高,极限氧指数在25.8～29.3,玻璃化转变温度得到提高,在161～179℃;虽然初始分解温度比纯环氧树脂固化物低,但800℃残炭率可以达到26.5%,提高了36%;拉伸强度得到提高,在71～94 MPa,冲击强度可以达到14.36 kJ/m2,提高了14%.该固化体系具有较好的阻燃性能和热性能,同时具有较好的力学性能.     

Fabrication of high thermal stable cured novolac/Cloisite 30B nanocomposites by chemical modification of resin structure

Cloisite 30B as a modified kind of nanoclay was utilized for the formation of 3D network based on novolac resin with high thermal stable properties. Two types of phenolic resins including neat novolac (NR) and modified novolac resin were used to create a compatible matrix with nanoclay. For this purpose, NR modified with (3‐chloropropyl)triethoxysilane (CPTES) to form SiNR. For improvement of thermal behaviors, Cloisite 30B was dispersed in matrix via ultrasonic waves and cured with hexamethylenetetramine (HMTA) to form 3D network. X‐ray diffraction (XRD) analysis was used to measure the d‐spacing in intercalated systems and results indicated the optimum amount of clay for appropriate thermal properties. Investigation of the thermal properties of the samples by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the presence of Cloisite 30B in matrix resulted in much higher thermal stability and char yield with respect to modification of novolac resin originated from formation of 3D Si–O–Si network. Also, cured modified resin and its nanocomposites showed much higher thermal stability than cured NR and its nanocomposites. Such nanocomposite materials with high thermal stability have potential applications in advanced fields such electronic, industrial molds, coatings, adhesives, and aerospace composites.     

Oligo-fluoropolymer Modified Cycloaliphatic Epoxy Resins with Excellent Compatibility,Waterproof and Mechanical Properties for LED Encapsulation

An oligo-fluoropolymer(PFM) with functional cycloaliphatic epoxy and fluorinated groups was obtained via free radical polymerization and applied to the modification of cycloaliphatic epoxy resins(CE). The chemical structure of PFM was characterized by Fourier transform infrared(FTIR) spectroscopy, gel permeation chromatography(GPC) and nuclear magnetic resonance(NMR) spectroscopy, and the effects of different PFM concentrations(0.5%—6%, mass fraction) on the thermal resistance, mechanical properties, surface dewettability, light transmission, refractive index and various cured polymer properties were studied in detail. The DSC and TGA results demonstrate that the modified epoxy resins possess a higher thermal resistance than the neat epoxy resin. The improvements in the surface dewettability and water resistance are caused by the high crosslinking density and the enrichment of the oligo-fluorinated random copolymers dispersed in the matrix. The fracture surface morphologies of the thermosets were investigated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM). It was observed that the optical transmittance of the composites was maintained even though microphase separation occurred during the curing process. With respect to the corresponding properties of the neat epoxy resins, the 2 phr(parts per hundreds of resin) PFM thermoset exhibited relatively better comprehensive properties, making the cured material a good candidate for light-emitting diode(LED) encapsulation.     

Effect of internal mold release agent on flexural and inter laminar shear properties of carbon and glass fabric reinforced thermoset composites

The study is focused on thermoset composites reinforced with carbon and glass woven fabrics. Two types of thermoset resins, for example, epoxy and vinyl ester were used as the matrix. Varying concentrations of internal mold releasing (IMR) agent was used in the resin. The composites were cured both at room temperature and at 80°C. The flexural properties were studied using 3‐point bending test method. Further theinter‐laminar shear strength (ILSS) was investigated using the short beam shear strength test based on 3‐point bending. The flexural modulus of room temperature cured epoxy resin is higher than that of high temperature cured epoxy resin and cured vinyl ester resin. The flexural modulus is lowest for 1% IMR sample in epoxy system and the modulus for 0% and 2% epoxy are not significantly different. Lowest flexural strength and modulus can be observed for the combination of reinforcement and curing conditions for samples containing 1% IMR for the epoxy systems. Carbon fiber is found to be less compatible with the vinyl ester resin system and the addition of IMR to the resin degraded the properties further. Inter‐laminar shear strength for epoxy‐based composites is not much affected by presence of IMR, but in case of vinyl ester based composites there is a decrease in ILSS on addition of IMR agent. The study explains variation in flexural properties on addition of IMR and change of curing conditions. These results can be used for ascertaining variation in mechanical properties in real use.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.     

Preparation and characterization of bismaleimide/1,3-dicyanatobenzene modified epoxy intercrosslinked matrices

An intercrosslinked network of cyanate ester (CE)-bismaleimide (BMI) modified epoxy matrix system was made by using epoxy resin, 1,3-dicyanatobenzene and bismaleimide (N,N^′-bismaleimido-4,4^′-diphenyl methane) with diaminodiphenylmethane as curing agent. BMI-CE-epoxy matrices were characterised using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterised 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 cyanate ester into epoxy resin improves the toughness and flexural strength with reduction in tensile strength and 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 cyanate ester as well as BMI modified epoxy resin show an unimodal reaction exotherm. Electrical properties were studied as per ASTM method and the morphology of the BMI modified epoxy and CE-epoxy systems were studied by scanning electron microscope.