Dicyanate Ester Of Bisphenol Research Articles

The Created Excellent Thermal, Mechanical and Fluorescent Properties by Doping Eu3+-Complex-Anchored Carbon Nanotubes in Polycyanate Resins.

In the blending process of the composites, the clustering of MWCNTs under high concentration leads to poor dispersion and difficult complexing with luminescent elements. Cyanate ester resins (CERs) have a brittle network structure when cured caused by a conjugation effect that forms a strong emission peak in the ultraviolet-visible region and quenches the luminescent elements of the fluorescent nanofillers. In this paper, by anchoring of the Eu complex (Eu(TTA)3Phen, ETP) on a surface of longitudinal split unzipped carbon nanotubes (uMWCNTs); fluorescent nanoparticles were prepared as ETP anchor unzipper carbon nanotubes (ETP-uCNTs). Dicyanate ester of bisphenol E (CER-E monomer) is cured to polycyanurate at a lower temperature to achieve a high conversion, promoting a uniform blend with ETP-uCNTs, providing the fluorescence environment with high color purity. Studies show the ETP-uCNTs solve the agglomeration of MWCNTs and improve the interface binding ability. Compared with the pure CER-E, the tensile strength, bending strength and impact strength of CER-E/0.8 wt.% ETP-uCNT hybrid nanocomposites are increased by 94.6%, 92.8% and 101.1%, respectively. The carbon residue rate of CER-E/ETP-uCNTs is up to 47.14% at 800 °C, the temperature of the maximum reaction rate decreases by 67.81 °C, and the partial absorption of ultraviolet light is realized between 200 and 400 nm.

Silica subnanometer-sized nodes, nanoclusters and aggregates in Cyanate Ester Resin-based networks: Structure and properties of hybrid subnano- and nanocomposites

A series of the densely cross-linked Cyanate Ester Resins (CER)-based composites with 0.01–10wt.% silica, introduced via sol-gel process, were synthesized using dicyanate ester of bisphenol E (DCBE), tetraethoxysilane (TEOS) and γ-aminopropyltrimethoxysilane (APTMS). Their structure, molecular dynamics and properties are investigated by HAADF STEM, EDXS, DMA, DSC, and FTIR and Far-IR spectroscopies. The extremely high “constrained dynamics” effect and the most enhanced thermal, relaxation and elastic properties are revealed for the composites with ultralow silica contents, e.g., up to 0.1wt.%, in the absence of silica nano- or microclusters: increasing Tg by 50°C and dynamic modulus by 60% at 20°C and as much as forty times at 260°C are observed. EDXS analysis including getting the histograms of Si content shows that chemically embedded silica units are distributed quasi-regularly in nanovolumes of amorphous CER matrix in this case. The results obtained lead to conclusion that at ultralow silica contents only subnanometer-sized silica nodes may be generated within the CER network, i.e., the hybrid polymer subnanocomposites are formed. Formation of silica nanoclusters and, especially, their aggregates of hundreds nanometers in size at silica contents of 2–10wt.% results in their negative impact on the matrix properties.

Origin of the Rapid Trimerization of Cyanate Ester in a Benzoxazine/Cyanate Ester Blend

Blends of cyanate ester and benzoxazine have been independently studied by several researchers, and different reaction mechanisms were reported. Recently, we unexpectedly observe that gelation occurred in a 50 wt % methyl ethyl ketone solution of P-oda/BACY (1/1 mol/mol) blend after 24 h at 30 °C, in which P-oda is a 4,4′-oxyaniline/phenol-based benzoxazine and BACY is a dicyanate ester of bisphenol A. Previous studies suggest that the rapid trimerization of cyanate ester in the blend is related to the ring-opened structure of benzoxazine. However, the possibility of ring-opening polymerization for benzoxazine at 30 °C is rare. Therefore, it is highly likely that the catalytic effect results from the benzoxazine itself, not from the ring-opened structure of benzoxazine. Through IR and DSC analyses, we conclude that the tertiary amine of benzoxazine catalyzes the trimerization of cyanate ester, and we propose a three-step catalytic mechanism of benzoxazine for the trimerization of cyanate ester.

Formulation and physical properties of cyanate ester nanocomposites based on graphene

ABSTRACTWe report the thermal, mechanical, and diffusion properties of bisphenol E based polycyanurate nanocomposites with three forms of graphene derived from sequential processing of the same carbon nanostructure. Edge‐functionalized graphene nanoplatelets (GNP) were converted to graphene oxide (GO), then heated to produce thermally reduced graphene oxide (TRGO). All three reinforcements were individually mixed with the dicyanate ester of bisphenol E (LECy) at low loading levels and cured to form polycyanurate nanocomposites. GNP, with very low oxygen functionality, was incompatible with the cyanate ester, while the highly oxidized GO formed well‐dispersed (though not exfoliated) nanocomposites, with the TRGO forming a good dispersion on mixing but phase separating during cure. The addition of GO, and, to a lesser extent, TRGO, resulted in improved mechanical properties, particularly fracture toughness, with the addition of TRGO having a modestly negative effect on the glass transition temperature. Surprisingly, neither GO nor TRGO addition was effective at slowing down the diffusion of water in the polycyanurate, with the addition of both resulting in increased equilibrium moisture uptake. It thus appears that the trade‐off between dispersion and the required level of oxygen functionality acts in a manner to frustrate attempts at minimizing the permeation of water by addition of graphene‐based reinforcements. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1061–1070

Benzoxazine-based phosphinated bisphenols and their application in preparing flame-retardant, low dielectric cyanate ester thermosets

This work reveals a facile, one-pot synthesis of phosphinated bisphenols (1–2) from a nucleophilic addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) to diaminophenylmethane- and diaminophenylether-based benzoxazines (P-ddm and P-oda). A reaction mechanism including active hydrogen abstraction, ring-opening, and nucleophilic addition was proposed for the synthesis. Phosphinated dicyanate esters (3–4) were prepared based on bisphenols (1–2), and were copolymerized with a commercially available dicyanate ester of bisphenol A (BACY). The properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, water absorption, and flame retardancy of the resulting thermosets were evaluated. Experimental data show that incorporating (3–4) into BACY enhances the flame retardancy, dimensional stability and dielectric properties with small penalty to the thermal properties. A thermoset with Tg 241 °C, CTE 50 ppm per °C, Dk 3.01 (1 GHz), Td (5%), N2: 407 °C, and UL-94 V-0 rating can be achieved via this approach.

Preparation of phosphinated bisphenol from acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane and its application in high‐performance cyanate esters

AbstractWe reveal a route for the preparation of phosphinated bisphenol, 1,1‐bis(4‐hydroxyphenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (2), via a one‐pot reaction of 1,1,1‐tris(4‐hydroxyphenyl)ethane and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) in the catalysis of p‐toluenesulfonic acid. A two‐step reaction mechanism, acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane followed by nucleophilic addition of DOPO, is proposed for the synthesis. Based on (2), a dicyanate ester derivative, 1,1‐bis(4‐cyanatophenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (3) was prepared and co‐cured with a commercially available dicyanate ester, the dicyanate ester of bisphenol A (BACY). Experimental data show that incorporating (3) into BACY enhances the flame retardancy and dielectric properties with little penalty to the thermal properties. A thermoset with Tg 274 °C, coefficient of thermal expansion (CTE) 49 ppm/°C, Dk 3.04 (1 GHz), Td (5%,) N2: 435 °C, air: 424 °C, and UL‐94 V‐0 rating can be achieved via this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

Synthesis and characterization of cyanate ester and its blends with bisphenol dicyanate ester

A new keto-ene functionalized 1, 5-bis (4-hydroxyphenyl)penta-1,4-dien-3-one (HPDO) was prepared from p-hydroxy benzaldehyde and acetone using boric acid as a catalyst. The prepared bisphenol was converted into 1,5-bis (4-cyanatophenyl) penta-1,4-diene-3-one (CPDO) by reacting with cyanogen bromide (CNBr) in the presence of triethylamine. The synthesized bisphenol and the dicyanate ester were characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR) and elemental analysis (EA) techniques. CPDO was then blended with a commercial bisphenol-A dicyanate ester (BADCy) at different ratios (100:0, 75:25, 50:50. 25:75, 0:100) and the cure characteristics were studied. CPDO was found to be cured at a lower temperature than BADCy. The cyanate ester blends were cured at 373 K (30 min) → 423 K (30 min) → 473 K (60 min) → 523 K (3h). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to study the thermal properties. DSC studies show that the cure (peak) temperature of CPDO with and without a catalyst was found to be 408 K and 466 K respectively. The initial degradation temperature of the cured resins was found to be in the range from 701 K to 705 K. The Limiting Oxygen Index (LOI) value, determined by Van Krevelen’s equation, shows that these blends have good flame retardant properties.

Structure and Dynamic/compositional Heterogeneity in Polycyanurate—poly(Tetramethylene Glycol) Hybrid Networks

Structure and dynamics over the range from −150 to 300°C were studied in a series of polycyanurate‐poly(tetramethylene glycol) (PCN‐PTMG) hybrid networks. Wide‐angle x‐ray diffraction (WAXD), small‐angle x‐ray scattering (SAXS), laser‐interferometric creep rate spectroscopy (CRS), differential scanning calorimetry (DSC), and thermally stimulated depolarization currents (TSDC) techniques were applied. The networks were synthesized from the dicyanate ester of bisphenol A (DCEBA) and hydroxyl‐terminated PTMG with M n =1000, 2000 or 5000 g/mol and weight fraction of 10, 20, 30, and 40%. The noncrystalline structure and the pronounced structural nanoheterogeneity, depending on PTMG chain length and PCN‐PTMG ratio in the hybrid systems, were evidenced. Combined CRS/DSC analysis revealed a complex dynamics in these networks, in particular a dispersion of glass transitions in a wide temperature range. On this basis, the presence of nanodomains with different degrees of rigid cross‐linking (X CN→PCN), i.e., compositional nanoheterogeneity in these hybrids was shown. The results obtained turned out to be of applied interest because of a substantial increase in tensile strength because of arising microplasticity at low temperatures, and retaining some creep resistance, at low stresses, up to temperatures much higher the basic T g . In Commemoration of the Contributions of Professor Valery P. Privalko to Polymer Science.

Synthesis, characterization, and properties of novel epoxy resins and cyanate esters

AbstractWe synthesized a novel epoxy (dopotep) and cyanate ester (dopotcy) based on a phosphorus‐containing triphenol (dopotriol). The proposed structures were confirmed by IR, mass spectra, NMR spectra, and epoxy‐equivalent‐weight titration. The synthesized dopotep or dopotcy was copolymerized with diglycidyl ether of bisphenol A (DGEBA), 6′,6‐bis(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazineyl)methane (F‐a), or dicyanate ester of bisphenol A (BADCY). Thus, copolymers based on DGEBA/dopotep/diphenylmethane (ddm), F‐a/dopotep, BADCY/dopotcy, and DGEBA/dopotcy were developed. The thermal properties, dielectric properties, and flame retardancy of these copolymers were investigated. The curing kinetics of dopotep/ddm and dopotep/diamino diphenylsulfone were studied with differential scanning calorimetry. The microstructure of DGEBA/dopotcy was studied with IR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3487–3502, 2006

Structural/compositional nanoheterogeneity and glass‐transition plurality in amorphous polycyanurate–poly(tetramethylene glycol) hybrid networks

AbstractThe nanostructure and dynamics over the temperature range of −140 to 300 °C were studied in a series of polycyanurate (PCN)–poly(tetramethylene glycol) (PTMG) hybrid networks by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering, with a synchrotron radiation setup, and by differential scanning calorimetry (DSC) and laser‐interferometric creep rate spectroscopy (CRS) techniques, respectively. The networks were synthesized from the dicyanate ester of bisphenol A and hydroxyl‐terminated PTMG with a number‐average molecular weight of 1.000 g/mol; the PTMG content varied from 0 to 40 wt %, and the degree of its chemical incorporation into the PCN network changed from 78.8 to 97%. The noncrystalline structure and considerable structural nanoheterogeneity of the hybrid networks were shown. CRS/DSC analysis revealed a complicated dynamic behavior, that is, a wide dispersion of glass transitions in the hybrid networks due to the presence of nanodomains with different degrees of rigid crosslinking (i.e., compositional nanoheterogeneity). Besides the physical significance, the plurality of glass transitions found in the PCN–PTMG hybrid networks was also of practical interest because it resulted in increasing mechanical strength of the brittle PCN network due to microplasticity arising at room temperature and moderate temperatures and the retention of some rigidity and creep resistance at temperatures much higher than the basic glass‐transition temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3261–3272, 2005

Structure–thermal property relationships for polycyanurate–polyurethane linked interpenetrating polymer networks

Chemical structure and thermal-oxidative degradation of sequential IPNs based on crosslinked polyurethane (CPU) and polycyanurate network (PCN) have been studied. As a result of chemical interaction between monomer, dicyanate ester of bisphenol A (DCEBA) and CPU during PCN formation (polycyclotrimerization of DCEBA into CPU matrix), covalent bonding between the networks occurs, leading to creation of linked IPNs (LIPNs). The formation of a new hybrid network (HN) structure has been confirmed. The coexistence of CPU, PCN and HN structures in the LIPNs, confirmed by infrared spectroscopy and by the observation of degradation stages characteristic for each structure, depends on the ratio of the components. Three structures were found for the 90/10 CPU/PCN; HN and PCN were observed in the 70/30 LIPN and the hybrid network was the main structure detected for the 50/50 LIPN.

Synthesis, characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester

Multifunctional naphthalene-containing epoxy resins derived from 2,7-dihydroxylnaphthalene were synthesized and the intermediates were characterized by Fourier transform infrared spectroscopy, elemental analysis, and mass spectrometry. The cured products from naphthalene-containing epoxy resin and the dicyanate ester of bisphenol A (DCBA) exhibited a better Tg and a lower coefficient of thermal expansion than those of the commercial epoxy system. The glass transition temperature, thermal stability, and moisture absorption were found to increase with the epoxy functionality when naphthalene-containing epoxy resins were cured with DCBA. Thermogravimetric analyses revealed that the DCBA-cured system had a better thermal stability than that of the 4,4′-diaminodiphenylsulfone (DDS)-cured system. The addition of a metallic catalyst into the epoxy resin/cyanate ester system not only facilitated the cyclotrimerization of the cyanate ester but also the polyetherification of the epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1611–1622, 1999