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     

Preparation and properties of glass cloth‐reinforced polyimide composites with improved impact toughness for microelectronics packaging substrates

A series of glass cloth‐reinforced thermosetting polyimide composites (EG/HTPI) were prepared from E‐glass cloth (EG) and polyimide matrix resins. The polyimide resins were derived from 1,4‐bis(4‐amino‐2‐ trifluoromethyl‐phenoxy)benzene, p‐phenylenediamine, diethyl ester of 3,3′,4,4′‐benzophenonetetracarboxylic acid, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid. Based on the rheological properties of the B‐staged polyimide resins, the optimized molding cycles were designed to fabricate the EG/HTPI laminates and the copper‐clad laminates (Cu/EG/HTPI). Experimental results indicated that the EG/HTPI composites exhibited high thermal stability and outstanding mechanical properties. They had flexural strength of >534 MPa, flexural modulus of >20.0 GPa, and impact toughness of >46.9 kJ/m². The EG/HTPI composites also showed good electrical and dielectric properties. Moreover, the EG/HTPI laminates exhibited peel strength of ～ 1.2 N/mm and great isothermal stability at 288°C for 60 min, showing good potential for application in high density packaging substrates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Properties and structures of novel cyanate ester/organic rectorite nanocomposites

Organic rectorite (OREC) was applied to bisphenol A dicyanate ester (BADCy) resin to develop a novel BADCy/OREC system. The influence of OREC on the reactivity of BADCy was discussed. The morphologies of cured BADCy/OREC systems were investigated by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The static and dynamic mechanical properties as well as the hot water resistance of cured BADCy/OREC systems were evaluated. Results indicate that the addition of OREC can catalyze the reaction of BDACy resin. The intercalated structure and exfoliated structure of silicate platelets may be formed in the cured BADCy/OREC composites. The suitable amount of OREC canimprove the flexural strength, the impact resistance and the hot water resistance of cured BADCy. OREC can maintain the glass transition temperature (T_g) and have slight influence on the dielectric property of cured BADCy. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

高性能树脂基覆铜板的研究进展

对高性能新型环氧树脂、双马来酰亚胺、氰酸酯等热固性树脂及聚苯醚、聚四氟乙烯、聚酰亚胺等热塑性树脂基覆铜板的近况及发展进行了综述。对用于覆铜板的新型环氧树脂体系、环氧固化体系、环氧改性剂的应用进行了重点阐述,并指出发展覆铜板的关键是加强高性能树脂基体的研究,即研制具有高耐热性、优异介电性能、阻燃环保性、能阻挡紫外光和具有自动光学检测功能等特性的树脂是今后的发展方向。     

Mechanical properties of copper‐clad laminate using composite naphthalene–phenyl‐based epoxy as prepreg

A composite was prepared that contained diglycidyl ether of tetrabromobisphenol A (DGETBA) and 1,5‐di(2,3‐epoxypropoxy)naphthalene (A), 4,4′‐bis(2,3‐epoxypropoxy)benzylideneaniline (B), or 4,4′‐bis(2,3‐epoxypropoxy)biphenyl (C), and then was cured using different ratios of dicyandiamide (DICY). The results of DSC, TGA, coefficient of thermal expansion, dielectric constant, and dissipation factor testing of the composite epoxy resins were analyzed, and investigation of the copper‐clad laminate using the composite epoxy resins as prepreg was also performed. Additionally, moisture absorption, peel strength, arc resistance, comparative tracking index, and flammability of the copper‐clad laminate were examined. Clearly, some of the physical or mechanical properties of the composite and the copper‐clad laminate can be improved by optimal addition of naphthalene–phenyl‐based epoxy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1485–1492, 2005     

Modification of bisphenol A dicyanate ester by carboxyl‐terminated liquid butadiene‐acrylonitrile and its composites

Cyanate esters with excellent high‐temperature properties and easy processing are well known as good resin materials used in aerospace and electrical industries, but the drawback of brittleness limits their usage. In this study, carboxyl‐terminated liquid butadiene‐acrylonitrile (CTBN) was introduced to improve the toughness of bisphenol A dicyanate resin (BADCy), a typical kind of the cyanate esters. Fourier transform infrared spectroscopy and differential scanning calorimetry were employed to investigate the effects of CTBN on the curing behavior of BADCy; the results indicate that the addition of CTBN has a great influence on the curing behavior of BADCy at lower temperatures, but little at higher temperatures. Data from the thermogravimetric analysis and heat deflection temperature analysis showed that the thermal properties of the modified systems were poorer than that of pristine BADCy resin. On the basis of the scanning electron micrographs of the modified systems, toughening mechanism of the systems was discussed. Mechanical and dielectric properties of the cured resins and glass fiber‐reinforced composites were also studied. Modified systems exhibit attractive properties for the future applications in aerospace industries. POLYM. ENG. SCI. 46:581–587, 2006. © 2006 Society of Plastics Engineers.     

Preparation and properties of high‐performance polysilsesquioxanes/bismaleimide‐triazine hybrids

A novel kind of high‐performance hybrids (coded as POSS‐NH₂/BT) with significantly decreased curing temperature, lowered dielectric constant and loss, and improved thermal resistance were developed, which were prepared by copolymerizing bismaleimide with cage octa(aminopropylsilsesquioxane) (POSS‐NH₂) to produce POSS‐containing maleimide, and then co‐reacted with 2,2′‐bis(4‐cyanatophenyl) isopropylidene. The curing behavior and typical properties of cured POSS‐NH₂/BT were systematically investigated. Results show that POSS‐NH₂/BT hybrids have lower curing temperatures than BT resin because of the additional reactions between  OCN and amine groups. Compared with BT resin, all hybrids show improved dielectric properties. Specifically, hybrids have slightly decreased dielectric constants and similar dependence of dielectric constant on frequency over the whole frequency from 10 to 10⁶ Hz; more interestingly, the dielectric loss of hybrids is only 25% of that of BT resin at the frequency lower than 10⁵ Hz, whereas all hybrids and BT resin have almost equal dielectric loss when the frequency is higher than 10⁵ Hz. In addition, POSS‐NH₂/BT hybrids also show good thermal and thermo‐oxidative stability compared with BT resin. All these differences in macroproperties are attributed to the difference in chemical structure between POSS‐NH₂/BT hybrids and BT resin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High‐performance epoxy hybrid nanocomposites containing organophilic layered silicates and compatibilized liquid rubber

A mixture of two epoxy resins, tetraglycidyl 4,4′‐diaminodiphenyl methane and bisphenol‐A diglycidylether, cured with 4,4′‐diaminodiphenyl sulfone, was used as matrix material for high‐performance epoxy hybrid nanocomposites containing organophilicly modified synthetic fluorohectorite and compatibilized liquid six‐arm star poly(propylene oxide‐block‐ethylene oxide) (abbreviated as PPO). The hydroxy end groups of the poly(propylene oxide‐block‐ethylene oxide) were modified, yielding a six‐arm star PPO with an average of two pendant stearate chains, two phenol groups, and two hydroxy end groups. The alkyl chains of the stearate end groups played an important role in tailoring the polarity of the polymer. Its phenol end groups ensured covalent bonding between liquid polymer and epoxy resin. Two different organophilic fluorohectorites were used in combination with the functionalized PPO. The morphology of the materials was examined by transmission electron microscopy. The hybrid nanocomposites were composed of intercalated clay particles as well as separated PPO spheres in the epoxy matrix. As determined by dynamic mechanical analysis, the prepared composites possessed glass‐transition temperatures around 220°C. Although the tensile moduli remain unaltered, the tensile strengths of the hybrid materials were significantly improved. The relatively high fracture toughness of the neat resin, though, was not preserved for the hybrid resins. Scanning electron microscopy of the fracture surfaces revealed extensive matrix shear yielding for the neat resin, whereas the predominant fracture mode of the hybrid nanocomposites was crack bifurcation and branching. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3088–3096, 2004     

Synthesis of epoxy‐functionalized hyperbranched poly(phenylene oxide) and its modification of cyanate ester resin

High curing temperature is the key drawback of present heat resistant thermosetting resins. A novel epoxy‐functionalized hyperbranched poly(phenylene oxide), coded as eHBPPO, was synthesized, and used to modify 2,2′‐bis (4‐cyanatophenyl) isopropylidene (CE). Compared with CE, CE/eHBPPO system has significantly decreased curing temperature owing to the different curing mechanism. Based on this results, cured CE/eHBPPO resins without postcuring process, and cured CE resin postcured at 230°C were prepared, their dynamic mechanical and dielectric properties were systematically investigated. Results show that cured CE/eHBPPO resins not only have excellent stability in dielectric properties over a wide frequency range (1–10⁹Hz), but also show attractively lower dielectric constant and loss than CE resin. In addition, cured CE/eHBPPO resins also have high glass transition temperature and storage moduli in glassy state. These attractive integrated performance of CE/eHBPPO suggest a new method to develop high performance resins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Chemically stable polyphenylene ether microcapsules prepared using a facile method for the self‐healing of polymers

Chemically stable polyphenylene ether (PPO) microcapsules (MCs) filled with epoxy resins (PPO‐EP MCs) were prepared using low‐molecular‐weight PPO with vinyl end‐groups as shell wall and epoxy resins as core material using an oil‐in‐water emulsion solvent evaporation method. This method for synthesizing MCs with PPO shell walls is simple, convenient and novel, which can avoid the influence of processing parameters on the chemical stability of the epoxy resin core material. The resulting PPO‐EP MCs exhibit good chemical stability below 255 °C mainly owing to the absence of a polymerization catalyst of the epoxy resins. The initial thermal decomposition temperature of the MCs is about 275 °C. The MCs were embedded in a 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) thermosetting resin system. When processed at high temperature (up to 220 °C), the microencapsulated epoxy resins could be released from the fractured MCs to matrix crack surfaces and bond the crack surfaces. An amount of 8 wt% MCs restored 91 and 112% of the original fracture toughness of the BMI/BA matrix when heated at 220 °C/2 h and 80 °C/1 h + 220 °C/2 h, respectively. The MCs only slightly decreased the thermal property of the matrix. © 2016 Society of Chemical Industry     

Epoxy‐modified cyanate ester resin and its high‐modulus carbon‐fiber composites

Epoxy E51‐modified bisphenol A dicyanate (BADCy) and its high‐modulus carbon fiber (M40) reinforced composites were prepared in this research. The carbon‐fiber composites were prepared by autoclave molding. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy of BADCy‐E51 blend systems showed that polycyclotrimerization of BADCy primarily took place at low temperature. Epoxy group reacted with triazine ring group and produced oxazolidinone at high temperature. The data of mechanical properties, water absorption, and heat deflection temperature (HDT) of cured castings showed that the matrix system containing 95 wt% BADCy and 5 wt% E51 had optimum characteristics. Scanning electron microscopy (SEM) analysis of M40 fiber and the fracture surfaces of M40/BADCy‐E51 composite displayed that the adhesion between M40 fiber and BADCy was good though the surface of M40 was inert. The high retention of mechanical properties of M40/BADCy‐E51 composite after long‐term exposure to environmental conditions indicated that the M40/BADCy composite was suitable for space applications. POLYM. COMPOS., 27:402–409, 2006. © 2006 Society of Plastics Engineers     

Cyanate ester resin modified by phenolic resin containing diphenyl oxide segments with high molecular weight

To obtain modified cyanate ester (CE) with good comprehensive properties and low cost, a novel phenolic resin containing diphenyl oxide (MPF) with high molecular weight was synthesized from diphenyl ether, formaldehyde, methanol and phenol by a two-step process which differed from polyphenylene oxide (PPO) in structure. The curing reaction and properties of the modified 2,2-bis(4-cyanatophenyl) propane (bisphenol-A-based cyanate ester, BADCy) by MPF were investigated. It was found that the curing temperature of the modified CE was lower than that of the unmodified CE. When the ratio of MPF and BADCy was 3:7, the cured resin exhibited low dielectric constant (3.00), low dielectric loss (0.0062) and high impact strength (12.5 kJ/m²), and its T _d5% was 371 °C, being superior to CE in the comprehensive properties. When the content of MPF was above 30 %, MPF/BADCy had poor comprehensive properties. In order to improve MPF/BADCy with high content of MPF, epoxy resin (E51) was added. When the ratio of MPF, BADCy and E51 was 50:50:67, the cured resin exhibited low dielectric constant (2.96), dielectric loss (0.0078) and high impact strength (11.84 kJ/m²), and its T _d5% was 365 °C. Small content of MPF or the combination of E51 and MPF were good for BADCy to improve its comprehensive properties.     

Mahua‐oil‐based resins for the high‐temperature curing of fly ash coatings

We attempted to prepare medium‐oil‐length glycerol alkyds based on Mahua oil. Fatty acids were isolated from the oil and used in the preparation of alkyds by the fusion method. The resins were characterized by IR spectroscopic analysis. The physicochemical and film properties of these resins were also studied. IR analysis of the resins revealed the formation of phthalate esters showing characteristic peaks at 1720 cm^?1. The resin was modified with melamine formaldehyde, which cured at high temperatures. Alternatively, the resin was made to air dry with ester gum, and the curing behavior was studied. The suitability of these resins for high‐temperature curing fly ash coating applications was established. Coatings were formulated with these resins and with 40% fly ash as an extender. The coatings were characterized by standard techniques, particularly for their anticorrosive and antiabrasive properties. Resistance to corrosion was evaluated in humidity and in salt‐spray conditions. We conducted a high‐stress (two‐body) abrasion test to test the abrasive wear resistance of the coatings. The Mahua‐oil‐resin‐based fly ash coatings were suitable for application in moderately corrosive and abrasive environments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 110–120, 2003     

Preparation of high‐performance polyethylene via a novel processing method of combining dynamic vulcanization with a silane‐grafted water‐crosslinking technique

A novel processing method of combining dynamic vulcanization with the silane‐grafted water‐crosslinking technique to improve the comprehensive properties of polyethylene (PE) is reported. PE was grafted with vinyl triethoxysilane (VTEO) first, and then, N,N,N′,N′‐ tetragylcidyl‐4,4′‐diaminodiphenylmethane epoxy resin was dynamically cured in a PE‐g‐VTEO matrix through a twin‐screw extruder to prepare PE‐g‐VTEO/epoxy blends. Polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) was used as a compatibilizer to improve the interaction between PE‐g‐VTEO and the epoxy resin. The results show that the novel processing method improved the strength, stiffness, and toughness of the blends, especially the heat resistance of the blends, by the addition of the dynamically cured epoxy resin as the reinforcement. PE‐g‐MAH increased the compatibility between PE‐g‐VTEO and the epoxy resin, which played an important role in the improvement of the comprehensive properties of the blends. In addition, after treatments in both hot air and hot water, the comprehensive properties of blends were further improved, thanks to the further curing reaction of epoxy with PE‐g‐VTEO. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Low dielectric and flame‐retardant properties of thermosetting redistributed poly(phenylene oxide)

A curable low‐molecular‐weight poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) was prepared by the redistribution of regular PPO with maleic anhydride (MA) in toluene, using benzoyl peroxide as an initiator. The redistributed PPO (MA‐PPO), which contained alkene groups, was characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. The redistributed PPO oligomers with reactive double bonds were cured with triallylisocyanurate (TAIC) and/or a phosphorus‐containing allyl‐functionalized monomer (allyl‐DOPO). Electrical properties of cured resins were studied by using a dielectric analyzer. The glass transition temperatures were measured by dynamic mechanical analysis. The flame retardancy was determined by the UL‐94 vertical test. The effects of curing accelerator and the amounts of TAIC and allyl‐DOPO incorporated into the network on the dielectric properties, glass transition temperature, and flame retardancy of the resulting systems were investigated. The results indicated that MA‐PPO cured with TAIC exhibited low dielectric constants (2.23–2.58 at 1 GHz) and dissipation factors (0.0034–0.0039 at 1 GHz) but had high glass transition temperatures (171–197°C)_. The MA‐PPO/TAIC copolymerized with allyl‐DOPO could achieve a flame retardancy rating of UL‐94 V‐0 at about 1.35 wt % of phosphorus. The redistributed PPO/TAIC resins have potential applications in the fabrication of printed circuit boards. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers.     

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     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry