Synthesis,Characterization of Phosphorus ContainingDiamide-diimide-tetraamines Based on L-TryptophanAmino Acid and Their Effect on Flame Retardancy ofEpoxy Resins简

The curing behavior of diglycidyl ether of bisphenol-A(DGEBA) with different phosphorus containing diamidediimide-tetraamines(DADITAs) was studied by DSC. Eight DADITAs of varying structures were synthesized by reacting 1 mole of pyromellitic anhydride(PMDA)/3,3′-benzophenone tetracarboxylic dianhydride(BTDA)/1,4,5,8-naphthalene tetracarboxylic dianhydride(NTDA)/4,4′-oxydiphthalic anhydride(ODPA) with 2 mole of L-tryptophan(T) in a mixture of acetic acid and pyridine(3:2 V/V) followed by activaton with thionyl chloride and then condensation with excess of phosphorus containing triamines tris(3-aminophenyl) phosphine(TAP) and tris(3-aminophenyl) phosphine oxide(TAPO). DADITAs obtained by reacting PMDA/BTDA/NTDA/ODPA with L-tryptophan followed by condensation with TAP/TAPO were designated as PTAP, PTAPO, BTAP, BTAPO, NTAP, NTAPO, OTAP and OTAPO respectively. The structural characterization of synthesized DADITAs was done by FTIR,1H-NMR,13C-NMR,31P-NMR spectroscopic techniques and elemental analysis. Thermal stability of the isothermally cured epoxy was investigated using dynamic thermogravimetry analysis. The glass transition temperature(Tg) was highest in DGEBA cured using PTAP. All epoxy thermosets exhibited excellent flame retardancy, moderate changes in Tg and thermal stability. Due to presence of phosphorus in curing agents, all epoxy resin systems met the UL-94 V-0 classification and the limiting oxygen index(LOI) reached up to 38.5, probably because of the nitrogen-phosphorus synergistic effect.     

Cure behavior of diglycidylether of bisphenol A/trimethylolpropane triglycidylether epoxy blends initiated by thermal latent catalyst

Cure behaviors of diglycidylether of bisphenol A (DGEBA)/trimethylolpropane triglycidylether (TMP) epoxy blends initiated by 1 wt % N‐benzylpyrazinium hexafluoroantimonate (BPH) as a cationic latent catalyst were investigated using DSC and rheometer. This system showed more than one type of reaction and BPH could be excellent thermal latent catalyst without any co‐initiator. The cure activation energy (E_a) obtained from Kissinger method using dynamic DSC data was higher in DGEBA/TMP mixtures than in pure DGEBA. Rheological properties of the blend system were investigated under isothermal condition using a rheometer. The gel time was obtained from the analysis of storage modulus (G′), loss modulus (G″) and damping factor (tanδ). The crosslinking activation energy (E_c) was also determined from the Arrhenius equation based on the gel time and curing temperature. As a result, the crosslinking activation energy showed a similar behavior with that obtained from Kissinger method. And the gel time decreased with increasing TMP content, which could be resulted from increasing the activated sites by trifunctional epoxide groups and decreasing the viscosity of DGEBA/TMP epoxy blend in the presence of TMP. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2114–2123, 2000     

Thermal and mechanical interfacial properties of the DGEBA/PMR-15 blend system

In this work, the blend system of diglycidyl ether of bisphenol A and PMR-15 polyimide is investigated in terms of thermal and dynamic mechanical interfacial properties of the casting specimens. The thermal stabilities are studied by thermogravimetric and thermomechanical analyses, and the dynamic mechanical properties are carried out by dynamic mechanical analysis. The results show that the thermal stabilities based on the initial decomposition temperature, the integral procedural decomposition temperature, and the glass transition temperature are increased with increasing PMR-15 content. The crosslinking density (rho) of the blend system is increased at 10 phr of PMR-15, compared with that of neat epoxy. Mechanical interfacial properties measured in the context of critical stress intensity factor and critical strain energy release rate show similar behaviors with E(a) and rho, probably due to the increase in intermolecular interactions or hydrogen bondings in polymer chains.     

Cationic cure of epoxy resin initiated by methylanilinium salts as a latent thermal initiator

The effect of the novel N‐crotyl‐N,N‐dimethyl‐4‐methylanilinium hexafluroantimonate (CMH) initiator on cure kinetics and rheological properties of diglycidylether of bisphenol A (DGEBA) epoxy cationic system was investigated. From DSC measurements of the DGEBA/CMH system, it was found that this system exhibited excellent thermal latent characteristics at a given temperature and revealed complex cure behavior as indicated by multiple exotherms. The conversion and conversion rate of the DGEBA/CMH system increased with increasing the concentration of initiator, attributed to the high activity of CMH. Viscoelastic properties during gel formation of DGEBA initiated by CMH were investigated by rheological techniques under isothermal conditions. The gel time obtained from the modulus crossover point t(G′) = G″ was affected by a high curing temperature and the concentration of CMH, resulting in a high degree of network formation in cationic polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2397–2406, 2001     

Industrial cutting waste granite dust reinforced cardanol benzoxazine/epoxy resin hybrid composites for high-voltage electrical insulation applications

An attempt has been made to develop hybrid composites from benzoxazine monomer (C-ddm) hybridized with DGEBA epoxy resin (EP) and reinforced with varying weight percentages (20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt%) of glycidoxypropyltrimethoxy- silane (GPTMS) functionalized granite dust (GD) obtained from industrial granite cutting and polishing process in order to utilize them for electrical insulation applications. The thermal stability of granite dust reinforced poly(EP-co-C-ddm) composites was studied by TGA analysis. Among the composites samples studied, 100 wt% GD reinforced poly(EP-co-C-ddm) composites possess better thermal stability than that of other neat matrices and composites. Among the composites prepared using varying weight percentages of functionalized GD reinforcement, it was observed that 80 wt% GD reinforced poly(EP-co-C-ddm) composites possesses better hydrophobic character than that of other neat matrices and composites. The value of LOI calculated for neat matrix (poly[EP-co-C-ddm]) and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% GD reinforced composites was found to be 22, 28, 34, 40, 43 and 45 respectively. The 80 wt% GD reinforced poly(EP-co-C-ddm) composites possess the higher values of tensile strength and flexural strength of 47 MPa and 140 MPa, respectively than those of their samples. The values of electrical surface resistivity and electrical volume resistivity of all the neat matrices and GD reinforced polybenzoxazine composites were found to be in the order of 10¹² and 10¹³ respectively. The values of dielectric strength obtained from break down voltage (BDV) for neat matrix [poly(EP-co-C-ddm)] and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% of GD reinforced poly(EP-co-C-ddm) composites are 15.0, 15.5, 16.5, 17.0, 17.0 and 17.0 kV/mm, respectively. Data obtained from thermal stability, hydrophobic behavior and dielectric studies it was inferred that the hybrid polymer composites developed in the present work can be conveniently used in the form insulators, sealants, adhesives and matrices where application demands at high-performance industrial and engineering applications.     

Curing Kinetics and Thermal Stability of Diglycidyl Ether of Bisphenol‐A Using Mixtures of Heterocyclic Derivatives of Stannanes and 4,4′‐Diaminodiphenylsulfone

Curing kinetics of diglycidyl ether of bisphenol-A (DGEBA) in the presence of varying molar ratios of derivatives of stannanes to 4,4'-diaminodiphenylsulfone (DDS) was investigated by the dynamic differential scanning calorimetry. The derivatives were synthesized by reacting 1 mole of biguanide (B) with 1 mole of phenylethyltindihydride (PETH) or phenylmethyltindihydride (PMTH) or phenylbutyltindihydride (PBTH) and designated as BPETH or BPMTH or BPBTH respectively. These derivatives were characterized by elemental analysis and spectroscopic techniques such as IR, ¹H NMR, ¹³C NMR and ¹¹⁹Sn NMR. The mixtures of these derivatives to DDS at ratios of 0∶1, 0.25∶0.75, 0.5∶0.5, 0.75∶0.25 and 1∶0 were used to investigate the curing behaviour of DGEBA. The multiple heating rate method (5, 10, and 15 and 20 ℃•min^－1) was used to study the curing kinetics of epoxy resins. The thermal stability of the isothermally cured resins was also evaluated using dynamic thermogravimetry in a nitrogen atmosphere.