Preparation and properties of cyanate ester modified by epoxy resin and phenolic resin

Stiff and brittle cyanate ester (CE) resin was modified by copolymerizing it with epoxy resin (ER) and phenolic resin (PR) to improve its toughness and flexibility. The cure process of the modified CE resin was characterized by gel time curves and differential scanning calorimetry curves. The Fourier transform infrared spectra of the modified CE resin showed its chemical structure during the curing process. The mechanical properties, thermal behavior, dielectric properties, and morphology of the modified CE resins were investigated. The results showed that an increase in epoxy and phenolic resins resulted in improved flexibility while maintaining thermal stability. When the mass ratio of CE/ER/PR was 70 : 15 : 15 (w/w), flexural strength and impact strength of the modified CE resin increased from 113.6 MPa and 5.2 kJ/m² to 134.5 MPa and 16.7 kJ/m², respectively. Little of the thermal stabilityand dielectric properties was sacrificed in the modification of the CE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3150–3156, 2007     

Thermal degradation study of interpenetrating polymer network based on modified bismaleimide resin and cyanate ester

Interpenetrating polymer networks (IPNs) based on different ratios of a modified bismaleimide resin (BMI/DBA) and cyanate ester (b10) have been synthesized via prepolymerization followed by thermal curing. A systematic thermal degradation study of these new BMI/DBA‐CE IPN resin systems was conducted by thermogravimetric analysis at different heating rates both in N₂ (thermal stability) and in air (thermal‐oxidative stability). The cured BMI/DBA‐CE IPN resin systems show excellent thermal stability, which could be demonstrated by 5% weight loss temperature (T_5%) ranging between 409 and 423 °C, maximum decomposition rate temperature (T_max) ranging between 423 and 451 °C, and the char yields at 800 °C ranging from 37% to 41% in nitrogen at a heating rate of 10 °C min^?1. The apparent activation energy associated with the main degradation stage of the cured BMI/DBA‐CE IPN resin systems was determined using the Kissinger method. The obtained results provide useful information in drawing correlation between thermal properties and structure. © 2003 Society of Chemical Industry     

Liquid crystalline epoxy resin modified cyanate ester for high performance electronic packaging

A high performance modified cyanate ester (CE) resin system with significantly improved toughness, water resistance and dimensional stability was developed by copolymerizing CE resin with liquid crystalline epoxy resin (LCE) for electronic packaging. Four LCE/CE resins with different contents of LCE were prepared to systemically evaluate the effect of the content of LCE on the key properties of the modified system such as mechanical, dielectric and thermal properties as well as water resistance. Results reveal that the addition of LCE to CE can not only decrease the curing temperature of CE, but also significantly improve the integrated properties including mechanical and dielectric properties, thermal resistance as well as water resistance of cured resin. For example, compared with the whole exothermic peak of CE, that of LCE10/CE significantly shifts toward low temperature with a gap of about 15°C. On the other hand, the impact strength of cured LCE10/CE resin (22 kJ/m²) is about 2.1 times of that of CE resin; while the water absorption of the former is only 81.2% of that of the latter. In addition, cured LCE/CE resins also exhibit lower and more stable dielectric loss than CE resin over the whole frequency range from 10 to 10⁶ Hz. All these improvements in macro-performance by the addition of LCE to CE resin are not only ascribed to the cross-linked chemical structure, but also attributed to the rigid structure of liquid crystalline resin. The outstanding integrated properties of LCE/CE resins suggest great potential to be applied in the field of high performance electronic packaging.     

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     

Novel high‐performance wave‐transparent aluminum phosphate/cyanate ester composites

Advanced wave‐transparent composites are the key materials for many cutting‐edge industries including aviation and aerospace, which should have outstanding heat resistance, low dielectric constant and loss as well as good mechanical properties. A novel kind of high‐performance wave‐transparent composites based on surface‐modified aluminum phosphate AlPO₄(KH‐550) and cyanate ester (CE) was first developed. The dielectric and dynamic mechanical properties of AlPO₄(KH‐550)/CE composites were investigated intensively. Results show that AlPO₄(KH‐550)/CE composites have decreased dielectric loss and higher storage moduli than pure CE resin; in addition, the composites with suitable AlPO₄(KH‐550) concentration remain the outstanding thermal property and low dielectric constant of pure CE resin. The reasons attributing to these results are discussed from the effects of AlPO₄(KH‐550) on the key aspects such as morphology, curing mechanism, and interfacial adhesion of composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High‐performance polymeric materials with greatly improved mechanical and thermal properties from cyanate ester/benzoxazine resin reinforced by silane‐treated basalt fibers

This present article investigates the effect of silane‐treated basalt fibers (TBFs) on the morphological, mechanical and thermal properties of cyanate ester/benzoxazine (CE/BOZ) resin composites. The characterization was made using a scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), flexural test, impact strength (IS) test, microhardness test, dynamic scanning calorimetry, and thermogravimetric analysis. The mechanical test results inferred the distinctive improvements in the values of the flexural strength and modulus, IS, and microhardness of the CE/BOZ composites. The thermal stabilities in terms of the T_g, T_5%, T_10%, and T_HRI were appreciably improved and were higher than those of the pure CE/BOZ resin. Data from the SEM and FTIR tests ascertained the good dispersion and adhesion between the TBFs and the resin matrix, which might be behind the significant enhancement in the ultimate performances of the composites, with respect to the distinguished properties of BFs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46283.     

Preparation and properties of maleimide‐functionalized hyperbranched polysiloxane and its hybrids based on cyanate ester resin

A new hyperbranched polysiloxane containing maleimide (HPMA) was synthesized through the reaction between N‐(4‐hydroxyphenyl) maleimide and 3‐glycidoxypropyltrimethoxysilane, which was then used to prepare cyanate ester (CE) resin‐based hybrids (coded as HPMAx/CE, where x is the weight fraction of HPMA in the hybrid). The curing behavior of uncured hybrids and the typical properties (impact strength and dielectric properties) of cured hybrids were systemically investigated. Results show that the performance of hybrids is greatly related with the content of HPMA. Hybrids have obviously lower curing temperature than CE, overcoming the poor curing characteristics (higher curing temperature and longer curing time) of neat CE, for example, the curing peak temperature of HPMA20/CE is about 65°C lower than that of CE. In the case of cured resin and hybrids, the hybrids exhibit decreased dielectric constant and loss than CE resin; moreover, the former also exhibits lower water absorption than the latter. Specifically, the dielectric loss of HPMA15/CE hybrid is only about 27% of that of neat CE resin. In addition, the hybrids with suitable contents of HPMA have significantly improved impact strengths. The overall improved properties suggest that HPMAx/CE hybrids have great potential in applications needing harsh requirements of curing feature, dielectric properties, and toughness. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

E-51环氧树脂改性双酚A型氰酸酯树脂的研究

采用示差扫描量热法(DSC)、傅里叶变换红外光谱(FTIR)研究了E-51环氧树脂改性双酚A型氰酸酯树脂(BADCy)体系的反应活性、反应机理及固化工艺,通过TGA分析了不同含量E-51环氧树脂改性BADCy后固化物的热性能,并测定了体系的吸水率及力学性能。结果表明,随着E-51环氧树脂用量的增加,BADCy改性体系的反应活性逐渐提高,固化温度逐渐降低;用环氧树脂改性BADCy生成了恶唑烷酮等芳杂环结构,降低了氰酸酯树脂体系的三嗪环交联密度,增加了体系的韧性;改性后材料的起始热分解温度均在380℃以上,吸水率均低于2%。     

Morphological,mechanical and thermal properties of cyanate ester/benzoxazine resin composites reinforced by silane treated natural hemp fibers

This present study deals with the reinforcement of thermosetting resin blends composed of cyanate ester (CE) and benzoxazine (BOZ) resins with natural hemp fibers (NHFs). These NHFs were initially treated by using a silane coupling agent (SCA) in order to chiefly enhance their distributions as well as adhesions within the CE/BOZ resin matrix, then incorporated with various weight amounts ranging from 5 wt% to 20 wt% with a regular interval of 5 wt%. The obtained results showed that at the maximum treated fiber loading (20 wt%), distinctive enhancements in the mechanical properties in terms of flexural strength and microhardness were obtained. Besides, the thermal stability and glass transition temperature (T_g) were appreciably enhanced and were higher than those of the pure CE/BOZ resin properties. With respect to the astonishing properties of the NHFs, these enhancements could be possibly due to the good dispersion and adhesion of the treated NHFs inside the CE/BOZ resin achieved upon using the SCA. Therefore, we believe herein that these renewable and cheap NHFs have considerable potential to be used as reinfocer materials for CE/BOZ resin composites to be used in various industrial sectors.     

Investigation on curing reaction of phthalonitrile resin with nanosilica and the properties of their glass fiber-reinforced composites

In this work, Phthalonitrile containing benzoxazine (BA-ph) and Bisphenol A based cyanate ester (CE) were chosen as the matrix resin. Various amount of nano-SiO₂ was incorporated into BA-ph/CE and their glass fiber-reinforced composite laminates were fabricated. Curing reaction and processability of BA-ph/CE/SiO₂ blends were studied by differential scanning calorimetry and dynamic rheological analysis. Results showed that BA-ph and CE exhibited good processability and curing reaction of BA-ph/CE was not obviously affected by SiO₂. Scanning electron microscope images of the composites showed that SiO₂ particles were well dispersed in BA-ph/CE matrix. Moreover, SiO₂ could act as physical crosslinking points and diluent in matrix as well as between the glass fibers to improve the mechanical properties of composite laminates. As the results of dynamic mechanical analysis and thermogravimetry analysis, composite laminates possessed satisfactory T_g and good thermal stability. With incorporation SiO₂ particles into matrix resin, dielectric constant and dielectric loss of BA-ph/CE/SiO₂/GF composites were increased and showed frequency dependence.     

A novel cyanate ester resin/microcapsules system

Poly(urea‐formaldehyde) microcapsules filled with epoxy resins(MCEs) were applied to bisphenol A dicyanate ester (BADCy) resin to develop a novel BADCy/MCEs system. The effects of MCEs on the viscosity and the reactivity of BADCy were investigated. The mechanical properties and the hot water resistance of cured BADCy/MCEs systems were evaluated. The morphologies of the cured systems were characterized using a scanning electron microscope. The thermal property of cured systems was investigated using thermogravimetric analysis. The results indicate that MCEs may influence the reaction of BDACy. The proper addition of MCEs can significantly improve the mechanical property and the hot water resistance of cured BADCy resin. MCEs have a negative influence on the initial thermal decomposition temperature (T_d) of cured BADCy resin. POLYM. COMPOS., 2010. © 2008 Society of Plastics Engineers.     

Toughening modification of cyanate ester with amino-terminated polyoxypropylene

An amino-terminated polyoxypropylene (DA2000) was used to modify a bisphenol A-type cyanate ester resin (BADCy). A series of BADCy/DA2000 resins with different DA2000 contents were prepared and investigated by mechanical tests, dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The results of mechanical tests demonstrated that the addition of DA2000 improved the bending and tensile strength of the modified resins. Compared with those of pure BADCy, the K _IC and G _IC values of the modified resins increased, indicating an improvement in toughness of the resin system. The DMA curves of modified resins showed that the storage moduli dropped with the increase in temperature and the T _g values decreased with the increase in modifier content. Simultaneously, the moduli showed different changing trend at different temperature stages, indicating the existence of phase separation, which was also demonstrated by the fracture morphologies. At 20 wt% of DA2000 content, the fracture surface showed its characteristic strong ductile tear. Based on the above results, it was concluded that the –NH₂ groups of DA2000 reacted with the –OCN groups of triazine ring to form flexible segments, which were embedded into the main chains of the curing network; the distance between the triazine rings increased, the cross-link density decreased and the yield deformation of the system was enhanced. Meanwhile, DA2000 reacted with BADCy monomers to form linear macromolecular chains, which interpenetrated into the network matrix, and enhanced the plastic deformation of the system. The formation of flexible segments, low cross-link density and the yield and plastics properties led to toughened cyanate ester (CE) resins.     

酚醛型环氧树脂改性氰酸酯复合材料性能的研究

通过DSC分析,粘度、介电性能、力学性能及耐油性测试对酚醛型环氧树脂改性氰酸酯树脂复合材料的性能进行了研究。结果表明,改性氰酸酯树体系在70～160℃具有较低的粘度,理想工艺是在125～130℃下30～45min后开始加压;改性氰酸酯树脂表观活化能和反应级数分别为60.81kJ/mol和0.8846。改性氰酸酯复合材料具有良好的力学性能、介电性能和耐油性能。     

Preparation and properties of KH550-Al2O3/PI–EP nanocomposite material

First, polyimide (PI)–epoxy resin (EP) polymer matrix was prepared from 3,3′-diethyl-4,4′-diamino diphenyl methane (DEDADPM), benzophenone tetracarboxylic acid dianhydride (BTDA) and epoxy resin (E-51), through thermal imide process. Then, the nanometer alumina (Al₂O₃) modified by the coupling agent, (3-aminopropyl)triethoxysilane (KH550), was doped into the PI–EP polymer matrix, using an in situ sol–gel method to prepare a series of KH550-Al₂O₃/PI–EP nanocomposite materials based on different KH550-Al₂O₃ contents. Fourier transform infrared spectroscopy (FTIR) indicated that in the presence of chemical reaction between poly(amic acid) and epoxy resin, an imide ring was formed, the thermal imidization reaction of the materials was completed and the KH550-Al₂O₃ had doped into the PI–EP polymer matrix. The heat-resistance, dielectric specification and mechanical properties of KH550-Al₂O₃/PI–EP nanocomposite materials were evaluated. The results showed that the decomposition temperatures were ranged between 438 and 450 °C, dielectric constant and dielectric loss were in the range of 3.32–3.71 and 1.5 × 10^?3–2.5 × 10^?2, respectively, and they all increased with the increase of KH550-Al₂O₃ content (0–10 wt%), but the shear strength first increased and then decreased, attained its maximum value of 10.64 MPa at 8 wt%, which was about 119 % higher than that of undoped material. The adhesive forces of nanocomposite materials were all at higher level (one or two levels). Thus, the overall performance of KH550-Al₂O₃/PI–EP nanocomposites was the best when the doping amount of KH550-Al₂O₃ was 8 wt%. The properties such as high heat-resistance, dielectric properties and ready attachment of impregnating varnish to steel plate with very high strength fully met the necessary requirement.     

Triazine reaction of cyanate ester resin systems catalyzed by organic tin compound: kinetics and mechanism

The mechanism and kinetics of the thermal cure reaction of two cyanate esters (CEs), 1,1′bis(4‐cyanatophenyl)ethane (AroCy L‐10) and bisphenol A dicyanate ester (BADCy), in the presence of dibutyl tin dilaurate (DBTDL) has been investigated using Fourier‐transform infrared spectroscopy (FTIR) and High‐performance liquid chromatography (HPLC). It was found that the organic tin compound (H₉C₄)₂Sn(NCO—R—OCN)₂, an active catalyst, has high catalytic efficiency in the polymerization of cyanate esters. The consuming rate of cyanate concentration showed a first‐order dependence on both active catalyst and the cyanate ester monomer concentration. The apparent activation energies (E_a) and frequency factors of both AroCy L‐10 and BADCy were calculated. A mechanism of cyclotrimerization was proposed, based on the kinetic data and FTIR spectra, which involves the formation of an active catalyst and the catalysis of the active catalyst. Copyright © 2004 Society of Chemical Industry     

New composites with high thermal conductivity and low dielectric constant for microelectronic packaging

Three composites based on cyanate (CE) resin, aluminum nitride (AlN), surface‐treated aluminum nitride [AlN(KH560)], and silicon dioxide (SiO₂) for microelectronic packaging, coded as AlN/CE, AlN(KH560)‐SiO₂(KH560)/CE, and AlN‐SiO₂/CE composite, respectively, were developed for the first time. The thermal conductivity and dielectric constant of all composites were investigated in detail. Results show that properties of fillers in composites have great influence on the thermal conductivity and dielectric constant of composites. Surface treatment of fillers is beneficial to increase the thermal conductivity or reduce dielectric constant of the composites. Comparing with binary composite, when the filler content is high, ternary composites possess lower thermal conductivity and dielectric constant. The reasons leading to these outcomes are discussed intensively. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Low‐temperature cure high‐performance cyanate ester resins/microencapsulated catalyst systems

The encapsulated catalyst can be released under stimulation conditions to control the polymerization reaction. In this study, poly(urea‐formaldehyde) (PUF) microcapsules (MCs) filled with dibutyltin dilaurate (DBTDL) catalyst (PUF/DBTDL MCs) were applied to bisphenol A dicyanate ester (BADCy) resins to develop a novel low temperature cure high performance BADCy/MCs systems. The effect of PUF/DBTDL MCs on the reactivity of BADCy was investigated. The mechanical property, the thermal property, the water uptake, and the dielectric property of cured BADCy/MCs resin systems were discussed in detail. Results indicate that roughly varying the content of the encapsulated DBTDL can easily and safely adjust the polymerization temperature. The BADCy systems with proper content of MCs cured at low temperature show excellent mechanical property, good thermal property, low water uptake, and low dielectric property. When the content of MCs is 0.125 wt%, the cured BADCy/MCs system has the optimal integrated properties owing to the formation of more uniform crosslinked structure and high conversion of cyanate ester (? OCN) groups resulting from the slow release of DBTDL catalyst through the wall shell under heating condition. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Nano-Si3N4/epoxidized silane/cyanate ester composites for electronic packaging

A novel kind of high performance composite of nano-Si₃N₄/epoxidized silane/cyanate ester (nano-Si₃N₄/ESi/BCE) has been developed. The mechanical, thermal and dielectric properties of the composite were investigated. The impact and flexural strength values of the nano-Si₃N₄/ESi/BCE system are 15.7 kJ/m² and 114.2 MPa, respectively, which are increased by about 56 and 21 % compared with those of pure BCE resin, respectively. The glass transition temperature of the nano-Si₃N₄/ESi/BCE system is 278.7 °C, which is nearly 30 °C higher than that of pure BCE resin. In addition, nano-Si₃N₄/ESi/BCE system also exhibits lower and more stable dielectric loss than pure BCE resin over the testing frequency from 10 to 50 MHz. All these improvements of properties are closely correlated to the synergistic effects between nano-Si₃N₄ and ESi in the BCE matrix. The novel nano-Si₃N₄/ESi/BCE system with the outstanding integrated properties shows great potentialities to be applied in the field of electronic packaging.     

环氧树脂改性氰酸酯树脂的研究

在保持氰酸酯树脂优良介电性能的前提下,用E44环氧树脂与双酚A型二氰酸酯共聚来改善氰酸酯树脂的力学性能。采用DSC研究了纯氰酸酯树脂、环氧树脂含量不同的共聚物的固化过程,发现环氧树脂能降低共聚体系固化温度。力学性能测试结果表明:环氧树脂对氰酸酯起到了增韧作用,当含量为30%时,拉伸强度、弯曲强度和压缩强度提高的幅度最大。断面SEM表明:环氧树脂的加入,使树脂体系韧性明显提高,不仅有大量韧性断裂纹出现,而且还有方向相互垂直的断裂纹。介电常数测试结果显示:环氧树脂的加入对树脂体系介电常数有明显影响,但仍能保持在4.5左右。     

Performance of aluminum borate whisker reinforced cyanate ester resin

Aluminum borate whisker (AlBw) treated with γ‐methacryloxypropyltrimethoxy silane (KH550) and borate ester (BE4) was adopted to modify bisphenol A dicyanate/epoxy resin (BADCy/E‐51) system, in this article. The influence of coupling agent and content of whisker on reaction activity were investigated by gel time and differential scanning calorimeter (DSC) and the results showed that addition of whisker enhances reaction activity of BADCy/E‐51 system slightly. The dispersion of whisker in matrix and reinforcement mechanism was investigated by scanning electron microscope (SEM). Results reveal that whisker treated with BE4 had better dispersing than that treated with KH550 in resin. The thermal stability, mechanical properties, and hot–wet resistance of AlBw/BADCy/E‐51 resin system were also studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007