Synthesis and characterization of bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane/epoxy/glass fiber composites

Bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane was prepared by treating CNBr with bis(4‐hydroxy‐3,5‐dimethylphenyl)anisylmethane and blended with commercial epoxy resin in different ratios and cured at 120°C for 2 h, 180°C for 1 h, and postcured at 220°C for 1 h using diamino diphenyl methane as curing agent. Castings of neat resin and blends were prepared and characterized. The composite laminates were also fabricated with glass fiber using the same composition. The tensile strength of the composites increased with increase in cyanate content (3, 6, and 9%) from 322 to 355 MPa. The fracture toughness values also increased from 0.7671 kJ/m², for neat epoxy resin, to 0.8615 kJ/m², for 9% cyanate ester‐modified epoxy system. The 10% weight loss temperature of pure epoxy (358°C) was increased to 390°C by the incorporation of cyanate ester resin. The incorporation of cyanate ester up to 9% in the epoxy resin increases the T_g from 143 to 147°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis,cure kinetics,and thermal properties of the Bis(3‐allyl‐2‐cyanatophenyl)sulphoxide/BMI blends

A novel allyl functionalized dicyanate ester resin bearing sulfoxide linkage was synthesized. The monomer was characterized by Fourier Transform Infrared (FT‐IR) Spectroscopy, ¹H‐, and ¹³C Nuclear Magnetic Resonance (NMR) spectroscopy and elemental analysis. The monomer was blended with bismaleimide (BMI) at various ratios in the absence of catalyst. The cure kinetics of one of the blends was studied using differential scanning calorimetry [nonisothermal] and the kinetic parameters like activation energy (E), pre‐exponential factor (A), and the order of the reaction (n) were calculated by Coats‐Redfern method and compared with those calculated using the experimental Borchardt‐Daniels method. The thermal stability of the cured dicyanate, BMI, and the blends was studied using thermogravimetric analyzer. The initial weight loss temperature of dicyanate ester is above 380°C with char yield of about 54% at 800°C. Thermal degradation of BMI starts above 463°C with the char yield of about 68%. Inclusion of BMI in cyanate ester increases the thermal stability from 419 to 441°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of epoxy sizing of carbon‐fiber on the properties of carbon fiber/cyanate ester composites

The high modulus carbon fiber (M40J) sized by epoxy resin E51 and E20 reinforced bisphenol A dicyanate (2,2′‐bis(4‐cyanatophenyl) isopropylidene resin composite was prepared in order to investigate the influence of epoxy sizing of the fiber on the properties of the composite. Differential scanning calorimetry (DSC) and fourier transforms infrared (FTIR) analysis showed that epoxy resin have catalytic effect on cure reaction of cyanate ester. Mechanical properties of the composite revealed that M40J fiber sized by epoxy resin could improve the flexural strength and interlaminar shear strength of M40J/bisphenol A dicyanate composites. The micro‐morphology of the composite fractures was studied by means of scanning electron microscopy (SEM). Reduced flaws were observed in the M40J‐bisphenol A dicyanate interface when the sized fiber was used. Water absorption of the composites was also investigated. It was found that the water absorption descended at the initial boiling stage (12 h). POLYM. COMPOS, 27: 591–598, 2006. © 2006 Society of Plastics Engineers     

Study on phenolphthalein poly(ether sulfone)‐modified cyanate ester resin and epoxy resin blends

In this work, the phenolphthalein poly(ether sulfone) (PES‐C)‐modified cyanate ester (CE) and epoxy (EP) blends were prepared. This work mainly discusses the curing behaviors, fracture toughness, dynamic mechanical properties, and thermal and mechanical properties of the blends. The Fourier transform infrared and differential scanning calorimetric analyses are used to confirm the curing behaviors, demonstrating that the main reaction pathways are not varied with the addition of PES‐C, but the reaction rate could be evidently accelerated. The fracture morphologies of the blends are observed by Scanning electron microscope (SEM) and the fracture causes of the failed surface are also analyzed. With the addition of PES‐C, the modified blends display higher fracture toughness (K_Ic) and impact strength when compared with neat CE. Domain sizes of the blends first increase then decrease with the addition of PES‐C. The results of dynamic mechanical analysis and thermogravimetric analysis show that the T_g, storage modulus, and thermal stability of the crosslink network slightly decreases with the addition of PES‐C. The mechanical strength of blends with the addition of PES‐C is far better than that of the blends without PES‐C both at ambient temperature and elevated temperature. POLYM. ENG. SCI., 55:2591–2602, 2015. © 2015 Society of Plastics Engineers     

Catalytic effect of 2,2′‐diallyl bisphenol A on thermal curing of cyanate esters

Cyanate esters are a class of thermal resistant polymers widely used as thermal resistant and electrical insulating materials for electric devices and structural composite applications. In this article, the effect of 2,2′‐diallyl bisphenol A (DBA) on catalyzing the thermal curing of cyanate ester resins was studied. The curing behavior, thermal resistance, and thermal mechanical properties of these DBA catalyzed cyanate ester resins were characterized. The results show that DBA is especially suitable for catalyzing the polymerization of the novolac cyanate ester resin (HF‐5), as it acts as both the curing catalyst through depressing the exothermic peak temperature (T_exo) by nearly 100°C and the toughening agent of the novolac cyanate ester resin by slightly reducing the elastic modulus at the glassy state. The thermogravimetric analysis and dynamic mechanical thermal analysis show that the 5 wt % DBA‐catalyzed novolac cyanate ester resin exhibits good thermal resistance with T_d⁵ of 410°C and the char yield at 900°C of 58% and can retain its mechanical strength up to 250°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1775–1786, 2006     

Fire‐resistant cyanate ester–epoxy blends

The cure chemistry, thermal stability and fire behaviour of a series of fire‐resistant cyanate ester–epoxy blends were examined. The dicyanate and diepoxide of 1, 1‐dichloro‐2, 2‐bis(4‐hydroxyphenyl)ethylene (bisphenol‐C, BPC) were combined in various molar ratios and the reaction chemistry was monitored using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The fire behaviour of the BPC cyanate–epoxy blends was studied in flaming and non‐flaming combustion, using OSU calorimetry and pyrolysis‐combustion flow calorimetry (PCFC), respectively. Published in 2003 by John Wiley & Sons, Ltd.     

The study on poly(ether sulfone) modified cyanate ester resin and epoxy resin cocuring blends

Poly(ether sulfone) terminated with phenolic hydroxyl groups modified cyanate ester resin and epoxy resin cocuring blends were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, rheometry, and mechanical properties measurement. The results suggested that poly (ether sulfone) (PES) could accelerate the polycyclotrimerization reaction of cyanate ester and cocuring processes between cyanate ester and epoxy of modified blends because of the presence of phenolic hydroxyl groups at the end of the PES molecules. It was found that the evolution of the morphologies and complex viscosities of the modified blends sensitive to molecular weight and content of PES, the tensile strength and elongation at break of the modified blends were correlated with the morphologies of modified blends. Moreover, the evolution of complex viscosities of the modified blends also showed an exponential growth at the early stage of phase separation, which demonstrated experimentally that the coarsening processes of droplets of bisphenol‐A dicyanate and diglycidyl ether of bisphenol A and the final morphologies obtained in the blends modified with PES were affected by viscoelastic behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water uptake effects in resins based on alkenyl‐modified cyanate ester–bismaleimide blends

The analysis of cured resin blends comprising a commercial dicyanate, bismaleimide and a range of novel alkenyl‐substituted cyanates, to determine the chemical effects of long‐term exposure to water, is reported. The cured resin blends underwent accelerated water uptake by immersion at temperatures of 50 °C and 70 °C, for a period of 14–17 months. The presence of about 10–15% (by weight) of alkenyl‐substituted cyanate in the blend leads to a marked reduction in moisture absorption in comparison with the unmodified bismaleimide/cyanate blend containing a comparable amount of bismaleimide. All samples display non‐Fickian diffusion behaviour at both immersion temperatures, although this is most marked at the higher temperature. Thermogravimetric analysis was performed on alkenyl‐modified neat resin samples before and after the immersion period. The modified samples display thermal stabilities that are indistinguishable from cured resins that have not undergone immersion. Spectroscopy (near infrared Raman and mid‐infrared attenuated total reflectance) was performed on cured resin plaques to determine the sample composition as a function of modifier content. The elemental composition of the samples was also determined before and after the immersion period, and no significant variation in elemental composition was recorded for the modified samples. © British Crown Copyright 2001/DERA. Reproduced with the permission of Her Majesty's Stationery Office. Published for the SCI by John Wiley & Sons, Ltd.     

Properties of cyanate ester-cured epoxy/polyphenylene oxide blends as a matrix material for Kevlar fiber composites

Epoxy/polyphenylene oxide (PPO) blends were cured with multifunctional cyanate ester resin. The effects of the PPO content on the cure behavior in the cyanate ester-cured epoxy were investigated with Fourier transform infrared spectroscopy (FTIR). The cure reaction in the epoxy/PPO blends was faster than that of the neat epoxy system. FTIR analysis revealed that the cyanate functional group reactions were accelerated by adding PPO and that several co-reactions had occurred, such as cyanate-hydroxyl addition and epoxy-cyanate addition. This was caused by the reaction of cyanate ester with the PPO phenolic end-group and water yielding imidocarbonate and carbamate intermediate which can react with cyanate ester to form cyanurate. Then the cyanurate can react further with the epoxy resin. Thermal mechanical analysis showed that the thermal stability of the epoxy/PPO blends is improved by adding PPO. The morphology of the fiber-rich areas in the composite is different from that of the epoxy/PPO blend without Kevlar fiber. In the pure polymer blends with high PPO content (30 and 50 phr), phase separation and phase inversion were observed. In the composites, the majority of the epoxy resin migrates to the polar fiber surface, resulting in epoxy-coated fibers. So the interfacial shear strength (IFSS) between Kevlar fiber and the epoxy/PPO blends is almost the same as that between Kevlar fiber and neat epoxy. The presence of PPO does not affect the interfacial property in the epoxy/PPO/fiber composite. So the interlaminar shear strength (ILSS) increase with the PPO content is due to an increase in the composite's ductility or toughness.     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Mechanical properties of high temperature cyanate ester/BMI blend composites

A new Schiff base functionalized dicyanate ester was synthesized and the monomer was characterized by FTIR, ¹H-NMR, ¹³C-NMR and elemental analysis techniques. This prepared dicyanate ester with catalyst was then blended with BMI resin at different ratios by solution technique. The composites were made by impregnating the fibers with the blend solution followed by curing at various time-temperature schedules. The mechanical properties of the blend composites were tested. The fiber volume fraction of the composites were found to be in the range 41 ± 3%. The mechanical properties such as tensile modulus (32–35 GPa), flexural modulus (56–59 GPa) and Mode I fracture toughness (G_IC = 104–136 J/m²) and impact response (1,121–1,218 J/m) were found to increase with increasing cyanate ester content in the Cy/BMI blends. From the DMA study it was observed that as the cyanate content increases from 3 to 9% in the blend the tan δ value increases from 0.112 to 0.126 and the storage modulus decreases from 24,750 to 22,870 MPa indicating that the crosslink density of the blends decreases. The SEM analysis shows the absence of phase separation. Moisture absorption and chemical resistance of the blend composites increase with increasing cyanate content. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Synthesis and properties of novel 4,4′‐biphenylene‐bridged flame‐retardant cyanate ester resin

The bisphenol‐containing 4,4′‐biphenylene moiety was prepared by the reaction of 4,4′‐bis(methoxymethyl) biphenyl with phenol in the presence of p‐toluenesulfonic acid. The bisphenol was end‐capped with the cyanate moiety by reacting with cyanogen chloride and triethylamine in dichloromethane. Their structures were confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. Thermal behaviors of cured resin were studied by differential scanning calorimetry, dynamic mechanical analysis, and TGA. The flame retardancy of cured resin was evaluated by limiting oxygen index (LOI) and vertical burning test (UL‐94 test). Because of the incorporation of rigid 4,4′‐biphenylene moiety, the cyanate ester (CE) resin shows good thermal stability (T_g is 256°C, the 5% degradation temperature is 442°C, and char yield at 800°C is 64.4%). The LOI value of the CE resin is 42.5, and the UL‐94 rating reaches V‐0. Moreover, the CE resin shows excellent dielectric property (dielectric constant, 2.94 at 1 GHz and loss dissipation factor, 0.0037 at 1 GHz) and water resistance (1.08% immersed at boiling water for 100 h). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

双酚A二氰酸酯/环氧树脂固化共混物结构的红外光谱研究

通过熔融共混制备了双酚A二氰酸酯/双酚A二缩水甘油醚环氧树脂、双酚A二氰酸酯/酚醛环氧树脂两种共混物。用红外光谱研究了组分比对两类共混物各种基团相对含量的影响。结果表明,随着共混物中环氧量的增加,芳醚的吸收会由于共聚产物的增加而出现蓝移,酚醛环氧树脂中的酚羟基能影响共聚产物的生成;环氧量较大的氰酸酯/酚醛环氧村脂共混物生成了相当含量的酚-氰酸酯加成物,这使得共聚产物相对含量的计算变得困难。     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis and characterization of epoxy/amine terminated amide‐imide‐imide blends

A new amine terminated amide‐imide (ATAI) was synthesized by the polycondensation reaction of tetrimide dicarboxylic acid containing bulky m‐chloro phenyl pendant with p‐phenylene diamine. The structure of all the prepared compounds were confirmed by FTIR,¹H‐NMR and ¹³C‐NMR techniques. This new diamine was then used to cure epoxy resin namely diglycidyl ester of bisphenol‐A and the cure reaction was studied by Differential scanning calorimetry. The cured blends show better thermal properties. The T_g of the epoxy resin was increased from 134°C to 156°C on addition of 6% of ATAI. The DMA results indicate that the polymer blend with 8% ATAI composition has higher storage modulus compared to 3% and 6% ATAI composition. The polymer blends with 3% and 6% ATAI composition have higher crosslinking density and lower intersegmental and intrasegmental friction coefficients than 8% ATAI composition. In the DMA curves an increase in the peak half‐width was observed with increasing ATAI composition, indicating the possibility of the existence of more than one phase with increasing ATAI concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of epoxy addition on the thermal,mechanical, and dielectrical properties of polycyanurate films

In the study, polycyanurate (PCN)/epoxy resin (ER) blends are prepared to enhance the physical properties of cyanate ester resins. The effects of curing schedule and blend composition on their thermal, mechanical, and dielectrical properties of cured PCN/epoxy blend films are examined. FTIR analysis of the cured blend films exhibits the expected cyanurate and oxazolidinone peaks in all blend compositions except the film thermally treated for 1 h in the presence of 1% phenol. TGA results show that the thermal stability decreases with epoxy content in the blend film. From SEM analyses, it is observed that all films have very dense, smooth, and bubble free surface without phase separation. For the pure PCN, the dielectric constants are found to be 3.54–5.91 in the range of 10^?1–10⁷ Hz between 20°C and 200°C. PCN/epoxy blends up to 50% epoxy resin show a good stability of dielectric constant in this frequency band for 200°C, which is close to the dielectric constant of the homopolymerized PCN. Beyond this percentage of epoxy resin, dielectric constants of PCN/epoxy blends greatly increase at low‐frequency region (0.1–10³ Hz) due to the interfacial polarization governed by Maxwell–Wagner–Sillars effect. POLYM. ENG. SCI., 58:820–829, 2018. © 2017 Society of Plastics Engineers     

Synthesis and properties of fluorinated biphenyl‐type epoxy resin

A novel fluorinated biphenyl‐type epoxy resin (FBE) was synthesized by epoxidation of a fluorinated biphenyl‐type phenolic resin, which was prepared by the condensation of 3‐trifluoromethylphenol and 4,4′‐bismethoxymethylbiphenyl catalyzed in the presence of strong Lewis acid. Resin blends mixed by FBE with phenolic resin as curing agent showed low melt viscosity (1.3–2.5 Pa s) at 120–122°C. Experimental results indicated that the cured fluorinated epoxy resins possess good thermal stability with 5% weight loss under 409–415°C, high glass‐transition temperature of 139–151°C (determined by dynamic mechanical analysis), and outstanding mechanical properties with flexural strength of 117–121 MPa as well as tensile strength of 71–72 MPa. The thermally cured fluorinated biphenyl‐type epoxy resin also showed good electrical insulation properties with volume resistivity of 0.5–0.8 × 10¹⁷ Ω cm and surface resistivity of 0.8–4.6 × 10¹⁶ Ω. The measured dielectric constants at 1 MHz were in the range of 3.8–4.1 and the measured dielectric dissipation factors (tan δ) were in the range of 3.6–3.8 × 10^?3. It was found that the fluorinated epoxy resins have improved dielectric properties, lower moisture adsorption, as well as better flame‐retardant properties compared with the corresponding commercial biphenyl‐type epoxy resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Cure reaction and phase separation behavior of cyanate ester‐cured epoxy/polyphenylene oxide blends

The cure reaction and phase separation mechanism of a cyanate ester‐cured epoxy and its blends with polyphenylene oxide (PPO) were studied. An autocatalytic mechanism was observed for the epoxy and its blends. The reaction rate of the blends was higher than that of the neat epoxy at initial stage; however, the reached conversion decreased with PPO content. FTIR analysis revealed that the cyanate functional group reactions were accelerated by adding PPO and indicated that several coreactions have occurred. This was caused by the reaction of cyanate ester with the PPO reactive chain ends. But at a later stage of cure, the reaction could not progress further due to diffusional limitation of PPO. To understand the relationship between the cure kinetics and phase separation of the blends, the morphology of the blends during cure was examined. When the homogeneous epoxy/PPO blends with low PPO content (10 phr) were cured isothermally, the blends were separated by nucleation and growth (NG) mechanism to form the PPO particle structure. But at high PPO content (30 phr), the phase separation took place via spinodal decomposition (SD). SD is favored near critical concentration and high cure rate system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1139–1145, 2006