C. P. Reghunadhan Nair

Cyanate Ester Resins, Recent Developments

The search for advanced, high performance, high temperature resistant polymers is on the rise in view of the growing demand for polymer matrix composites that are to meet stringent functional requirements for use in the rapidly evolving high-tech area of aerospace. Cyanate esters (CEs) form a family of new generation thermosetting resins whose performance characteristics make them attractive competitors to many current commercial polymer materials for such applications. The chemistry and technology of CEs are relatively new and continue to evolve and enthuse researchers. The CEs are gifted with many attractive physical, electrical, thermal, and processing properties required of an ideal matrix resin. These properties are further tunable through backbone structure and by blending with other polymer systems. The structure-property correlation is quite well established. Several new monomers have been reported while some are commercially available. The synthesis of new monomers has come to a stage of stagnation and the present attention is on evolving new formulations and processing techniques. The blends with epoxy and bismaleimide have attracted a lot of research attention and achieved commercial success. While the latter is now known to form an IPN, the reaction mechanism with epoxy is still intriguing. Extensive research in blending with conventional and high performance thermoplastics has led to the generation of key information on morphological features and toughening mechanisms, to the extent that even simulation of morphology and property has now become possible. Despite the fact that the resin and its technology are nearly two decades old, the fundamental aspects related to curing, cure kinetics, reaction modeling, etc. still evince immense research interest and new hypotheses continue to emerge.

Phosphazene–triazine cyclomatrix network polymers: some aspects of synthesis, thermal- and flame-retardant characteristics

Hydroxy phenyl-substituted cyclotriphosphazenes were synthesized by reacting hexachlorocyclotriphosphazene with sodium phenolate and monosodium bisphenolate. The derivatives, consisting of a mixture of multi-substituted and partly chain-extended cyclophosphazenes, with overall functionality close to the targeted values, were transformed into the cyanatophenyl derivative. Thermal curing of the latter gave phosphazene–triazine cyclomatrix network polymers with varying ratios of phosphazene and triazine rings in the matrix. Although they manifested diminished Tg, the cured polymers were more thermally stable and provided higher char residue in comparison to the polycyanurate derived from bisphenol-A dicyanate. The activation energies for thermal decomposition of the cyclomatrix networks increased with both phosphazene content and crosslink density, and showed a direct relationship with their thermal stability. The presence of phosphazene was conducive for enhancing the flame retardancy of the network. The flame retardancy improved with increase in crosslink density and char-yielding property of the polymer, which implied that the flame-retardant action was operative in the condensed phase. © 2000 Society of Chemical Industry

Thermal characteristics of addition-cure phenolic resins

Abstract The thermal and pyrolysis characteristics of four different types of addition-cure phenolic resins were compared as a function of their structure. Whereas the propargyl ether resins and phenyl azo functional phenolics underwent easy curing, the phenyl ethynyl- and maleimide-functional ones required higher thermal activation to achieve cure. All addition-cure phenolics exhibited improved thermal stability and char-yielding property in comparison to conventional phenolic resole resin. The maleimide-functional resins exhibited lowest thermal stability and those crosslinked via ethynyl phenyl azo groups were the most thermally stable systems. Propargylated novolac and phenyl ethynyl functional phenolics showed intermediate thermal stability. The maximum char yield was also given by ethynyl phenyl azo system. Non-isothermal kinetic analysis of the degradation reaction implied that all the polymers undergo degradation in at least two steps, except in the case of ethynyl phenyl azo resin, which showed an apparent single step degradation. The very low pre-exponential factor common to all polymers implied the significance of volatilisation process in the kinetics of degradation. Isothermal pyrolysis studies led to the conclusion that in the case of nitrogen-containing polymer, the pyrolysis occurs via loss of nitrogenous products, which is conducive for enhancing the carbon-content of the resultant char. FTIR spectra of the pyrolysed samples confirmed the presence of C–O groups in the char. XRD analysis of the partially carbonised polymers did not give any indication of crystallites except in the case of ethynyl phenyl azo system.

Kinetics of Alder-ene reaction of Tris(2-allylphenoxy)triphenoxycyclotriphosphazene and bismaleimides — a DSC study

Tris(2-allylphenoxy)triphenoxycyclotriphosphazene was reacted with three bismaleimides (BMI), viz. bis(4-maleimido phenyl)methane (BMM), bis(4-maleimido phenyl)ether (BME) and bis(4-maleimido phenyl)sulphone (BMS) via the Alder-ene reaction. The differential scanning calorimetric analysis of the blend manifested two distinct exotherms. The low temperature exothermic reaction was attributed to the Wagner-Jauregg reaction following the ene reaction and the strong exotherms at around 250–270°C to the cross-linking Diels–Alder reactions of the initially formed adducts. The Kinetic parameters, viz. activation energy (E) and pre-exponential factor (A) of the reactions were evaluated by Kissinger and Ozawa methods using the variable heating rate method. The kinetic data revealed that the Wagner-Jauregg reaction was disfavoured by electron-withdrawing nature of the BMI. The Diels–Alder reaction was facilitated by the electron-withdrawing nature of the bismaleimide. The activation energy for the first exothermic stage decreased and for the second major step increased on enhancing the stoichiometry of BMI in the blend for a given pair. The activation parameters served to predict the isothermal cure profiles of the blends and deduce the possible network structure under the given conditions of cure temperature and stoichiometry.

Sequential interpenetrating polymer networks from bisphenol A based cyanate ester and bimaleimide: Properties of the neat resin and composites

Blends of varying composition of a bisphenol A based cyanate ester—viz., 2,2-bis-(4-cyanatophenyl) propane (BACY)—and a bisphenol A based bismaleimide—viz., 2,2-bis[4-(4-maleimido phenoxy) phenyl] propane (BMIP)—were cured together in a sequential manner to derive bismaleimide–triazine network polymers. Enhancing the bismaleimide content was conducive for decreasing the tensile properties and improving both the flexural strength and fracture toughness of the cyanate ester-rich neat resin blends. Although DMA analyses of the cured blend indicated a homogeneous network for the cyanate ester dominated compositions, microphase separation occurred on enriching the blend with the bismaleimide. Addition of bismaleimide did not result in any enhancement in Tg of the blend. Interlinking of the two networks and enhancing crosslink density through coreaction with 4-cyanatophenyl maleimide impaired both the mechanical and fracture properties of the interpenetrating polymer network (IPN), although the Tg showed an improvement. Presence of the bismaleimide was conducive for enhancing the mechanical properties of the composites of the cyanate ester rich blend, whereas a higher concentration of it led to poorer mechanical properties due to the formation of a brittle interphase. The IPNs showed reduced moisture absorption and low dielectric constant and dissipation factor, the latter properties being independent of the blend composition.

Bisphenol A dicyanate–novolac epoxy blend: Cure characteristics, physical and mechanical properties, and application in composites

Reactive blends of bisphenol A dicyanate (BACY) and a novolac epoxy resin (EPN) were investigated for their cure behavior and the mechanical, thermal, and physical properties of the cocured neat resin and glass-laminate composites. Contrary to the apparent observation in DSC, the dynamic mechanical analysis confirmed a multistep cure reaction of the blend, in league with an established reaction path for similar systems. The cured matrix was found to contain both polycyanurate and oxazolidinone networks that existed in discrete phases exhibiting independent glass transitions in dynamic mechanical analysis (DMA). The flexible and less crosslinked oxazolidinone network contributed to enhanced flexural strength at the cost of the tensile strength of the neat resin. The increased resin flexibility was, however, not translated to the glass-laminate composite for which the flexural strength decreased with the oxazolidinone content, although the latter was conducive for rendering a stronger interphase. The presence of oxazolidinone adversely affected the thermal stability of the cured resin and the high-temperature performance of both neat resin and the composites.

Blends of bisphenol A-based cyanate ester and bismaleimide: Cure and thermal characteristics

A dicyanate ester, namely, 2,2-bis-(4-cyanatophenyl)propane, and a bismaleimide, namely, 2,2-bis[4-(4-maleimido phenoxy)phenyl]propane, possessing closely resembling backbone structures, were cured together to derive bismaleimide–triazine network polymers of varying compositions. The blend manifested a eutectic melting behavior at a 1 : 1 composition with a eutectic melting point of 15°C. The cure characterization of the blends was done by DSC and dynamic mechanical analyses (DMA). The near simultaneous cure of the blend could be transformed to a clear sequential one by catalyzing the dicyanate cure to lower temperature using dibutyl tin dilaurate. The two-stage, independent cure of the components of the blend evidenced in DSC was confirmed by DMA. The cure profile of the bismaleimide component predicted from the kinetic data derived from nonisothermal DSC was found to be in league with the isothermal DMA behavior. Both techniques led to optimization of the cure schedule of the blends. The cured polymers were characterized by FTIR and TGA. The cured blends underwent decomposition in two stages, each corresponding to the polycyanurate and polybismaleimide. Enhancing the bismaleimide component did not alter the initial decomposition temperature, but led to reduced rate of thermal degradation at higher temperature. Interlinking of the two networks and enhancing crosslink density through coreaction of the blend with 4-cyantophenylmaleimide unaffected the initial decomposition properties but was conducive for increasing the char residue significantly. Computation of activation parameters for the thermal decomposition of the polymers confirmed that the first step in the degradation of the blends is caused by the polycyanurate component.

Bis propargyl ether resins : synthesis and structure-thermal property correlations

Abstract Bis propargyl ethers of bisphenol-A, (BPA), bisphenol ketone (BPK) and bisphenol sulfone (BPS) were synthesised and characterised. These monomers were thermally polymerised to the corresponding poly (bischromenes). The cure behaviour, as monitored by differential scanning calorimetry, depended on the structure of the monomer. The non isothermal kinetic analysis of the cure reaction using four integral methods revealed that the presence of electron-withdrawing group did not favour the cyclisation reaction leading to formation of chromene, which precedes the polymerisation and this is in conformation to the proposed mechanism of polymerisation. Thus, the cure temperature and activation energy for the reaction increased in the order BPA

Solvent and kinetic penultimate unit effects in the copolymerization of acrylonitrile with itaconic acid

Abstract Copolymerization of acrylonitrile (AN) with itaconic acid (IA) in dimethylformamide (DMF) and DMF/water mixture was investigated at enhanced concentrations of the latter. Analysis of the copolymer composition revealed the existence of a marked penultimate unit effect with respect to radicals terminated in AN. The reactivity of IA was considerably less than that of AN, manifested as a negative reactivity ratio for the former. The rIA values ranging from −0.28 to −0.50 and rAN values ranging from 0.53 to 0.70, were obtained by Kelen–Tudos (KT) and extended KT methods. The penultimate reactivity ratios were determined by both linear and non-linear methods. The values ranged from r1=0.009 to 0.01, r1′=0.0015 to 0.0043, r2=0.54 to 0.69 and r2′=0.9 to 1.03. The reactivity of AN radical towards IA decreased about twofold when the latter formed the penultimate group. The penultimate model explained an acceptable rational feed-copolymer composition profile for the whole composition range. Addition of water decreased the reactivity of IA slightly. IA caused a decrease in the apparent copolymerization rate in agreement with the observed trends in the reactivity ratios; presence of water caused a further decrease in the rate of polymerization. A statistical prediction of monomer sequences based on reactivity ratios implied that IA existed as a lone monomer unit between the long sequences of AN units.

Catalysis of the cure reaction of Bisphenol A dicyanate. A DSC study

The kinetics of the thermal cure reaction of Bisphenol A dicyanate (BACY) in presence of various transition metal acetyl acetonates and dibutyl tin dilaurate (DBTDL) was investigated using dynamic differential scanning calorimetry (DSC). The cure reaction involved a pregel stage corresponding to around 60% conversion and a postgel stage beyond that. Influence of nature and concentration of catalysts on the cure characteristics was examined and compared with the uncatalyzed thermal cure reaction. The activation energy (E), preexponential factor (A), and order of reaction (n) were computed by the Coats–Redfern method. A kinetic compensation correction was applied to the data in both stages to normalize the E values. The normalized activation energy showed a systematic decrease with increase in catalyst concentration. The exponential relationship between E and catalyst concentration substantiated the high propensity of the system for catalysis. At fixed concentration of the catalyst, the catalytic efficiency as measured by the decrease in E value showed dependency on the nature of the coordinated metal and stability of the acetyl acetonate complex. Among the acetyl acetonates, for a given oxidation state of the metal ions, E decreased with decrease in the stability of the complex. A linear relationship was found to exist between activation energy and the gel temperature for all the systems. Manganese and iron acetyl acetonates were identified as the most efficient catalysts. In comparison to DBTDL, ferric acetyl acetonate proved to be a more efficient catalyst. The activation parameters computed using the Coats–Redfern method agreed well with the results from two other well known integral equations.