Study on Novel Epoxy Based Poly(schiff reagent)s

Abstract

Novel poly(schiff reagent)s (PSs) from diketo derivative of epoxy resin were synthesised and characterised. A series of epoxy resin based poly(schiff reagent)s were synthesised by reacting an epoxy resin, diglycidyl ether of bisphenol-A (DGEBA) with 4-amino acetophenone (4-AAP) in a 1:2 mole ratio to afford the corresponding diketo derivative, and subsequent reaction with various aliphatic diamines in the presence of a triethyl amine as a catalyst The resultant poly(schiff reagent)s were characterised by infrared spectroscopy (IR) and number average molecular weight (Mn) of PSs were estimated by non-aqueous conductometric titration. As produced, PSs having amine groups may act for curing of epoxy resins. Differential scanning calorimetric (DSC) curing kinetics of the epoxy resins viz., diglycidyl ether of bisphenol-A(DGEBA) and triglycidyl-p-amino phenol (TGPAP) have been investigated using PSs as a curing agent and triethyl amine as a catalyst. Thermal stability of the cured epoxy systems was studied by thermo-gravimetric analysis (TGA). The glass fiber reinforced composites of the produced PSs-epoxy system have been fabricated and were characterised by their mechanical properties and chemical resistance.     

Novel Epoxy Curing Agents from Epoxy Resin Based Dialdehyde Derivative

Abstract

A series of epoxy based curing agents were synthesised by the reaction of dialdehyde derivative 1, 1′-(1 -methylethylidene) di[4-{ 1-(1-imino-4-benzaldehyde)-2-propanolyloxy}] benzene of epoxy resin with a different aromatic diamines. The dialdehyde derivative was synthesised by the reaction of epoxy resin (DGEBA) with 4-amino benzaldehyde (4-ABA) in presence of triethyl amine (1% by wt. Of resin) as a catalyst. All this curing agents were characterised by their number average molecular weight (Mn), elemental analyses and infrared spectrophotometry (IR). As produced, polymers may act as a epoxy curing agent, the thermal characteristics of the synthesised PK-epoxy resin system were investigated by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Improvement of Elastic Modulus and Thermal Stability of Epoxy Resin Using New Curing Agents

New curing agents 2,5-diamino-1,3,4-thiadiazole (DATD) and N-(4-hydroxybenzal) N'(4′-hydroxyphenyl) thiourea (HHPT) were synthesised and characterized using FT-IR, 1H-NMR and 13C-NMR analysis. The curing reactions were studied for the epoxy resin diglycidyl ether of bisphenol-A (DGEBA) using new curing agents along with the conventional aromatic diamine 4,4′-diamino diphenyl methane (DDM) for comparison purpose. The curing profiles of DDM, DATD and DATD/HHPT towards DGEBA were examined by Differential Scanning Calorimetry (DSC). Elastic modulus and thermal stability of the cured resins were evaluated using DMA and TGA analysis. When compared with DDM and DATD, the DATD/HHPT curing system accelerated the curing rate due to the presence of phenol molecules in the HHPT. Furthermore, the DATD/HHPT-cured epoxy resin demonstrated higher elastic modulus along with better thermal stability.     

Amine-terminated poly(ethylene glycol) benzoate (ATPEGB)-modified epoxy: mechanical and thermal properties

Amine-terminated poly(ethylene glycol) benzoate (ATPEGB), synthesized from the esterification reaction of poly(ethylene glycol) (PEG) with 4-amino benzoic acid, was used to modify the toughness of bisphenol-A diglycidyl ether epoxy resin (DGEBA) cured with room temperature curing agent, triethylene tetramine. ATPEGB was characterized by FT-IR and H-NMR spectroscopies, viscosity measurements, solubility parameter calculation and molecular weight determination with gel-permeation chromatography (GPC). The modified epoxy network was evaluated for its impact, adhesive, tensile, flexural and thermal properties. Improvement in mechanical properties depends upon the concentration of the ATPEGB modifier. The optimum properties were obtained at 12.5 phr (parts per hundred parts of resin) concentration of the modifier. The ATPEGB modified cured epoxy was thermally stable up to 315°C. The morphology of cured epoxy was also analyzed by scanning electron microscopy (SEM) investigation of fracture surfaces.     

Hydroxyl terminated poly(ether ether ketone) with pendent methyl group toughened epoxy resin: miscibility, morphology and mechanical properties

The synthesis, processing, thermal and mechanical properties and fracture toughness of epoxy resin formulated with hydroxyl terminated poly(ether ether ketone) with pendent methyl group are reported. Hydroxyl terminated poly(ether ether ketone) oligomers based on methyl hydroquinone (PEEKMOH) were synthesised from methylhydroquinone and 4,4′-difluorobenzophenone in N-methyl-2-pyrrolidone. PEEKMOH oligomers with different molecular weights were synthesised and characterised. Blends of diglycidyl ether of bisphenol-A epoxy resin with PEEKMOH were prepared by melt mixing. The uncured blends were homogeneous and the T_g-composition behaviour was predicted using Fox, Gordon–Taylor and Kelley–Bueche equations. Reaction induced phase separation occurred in the blends on curing with 4,4′-diaminodiphenyl sulfone. Scanning electron microscopy studies revealed the two-phase morphology of the blends. Domain size of the blends increased with increase in PEEKMOH8 in the blends. Phase separation in the blends occurred by nucleation and growth mechanism. Infrared spectroscopic studies revealed that some of the epoxy groups were opened up by hydroxyl group of PEEKMOH. The tensile and flexural properties of the blends were comparable to that of neat epoxy resin and the properties were dependent on the composition of the blend and molecular weight of PEEKMOH used. Dynamic mechanical analysis revealed two glass transition temperatures corresponding to epoxy rich and thermoplastic rich phases. The crosslink density of epoxy resin decreased with the addition of PEEKMOH to epoxy resin. The blends exhibited superior fracture toughness compared to unmodified epoxy resin. The increase in fracture toughness was due to local plastic deformation of the matrix, crack path deflection and crack pinning. The thermal stability of amine cured epoxy resin was not affected by the incorporation of PEEKMOH into the epoxy resin.     

Novel Interacting Blends of Unsaturated Polyester-s-Triazine and Epoxy Resin

2-(4-ethyl-1-piperazinylo)-4,6-bismaleatedethylamino-1,3,5-triazine (EBT) was prepared by the reaction of 2-(4-ethyl-1-piperazinylo)-4,6-bishydroxyethylamino-1,3,5-triazine and maleic anhydride. The EBT derivative was characterized by elemental analysis, acid value and spectral studies.

EBT was then polycondensed respectively with three commercial epoxy resins, namely diglycidyl ether of bisphenol-A (DGEBA), diglycidyl ether of bisphenol-F (DGEBF) and diglycidyl ether of bisphenol-C (DGEBC). The resultant polymers are designated as unsaturated polyester-s-triazine (UPETs) and were characterized by elemental analysis, spectral study, molecular weight determination, differential scanning calorimeter (DSC)and thermogravimetry. The interacting blends of UPETs with DGEBA epoxy resin was made at stoichiometric ratio. The blending of these systems was monitored on a differential scanning calorimeter (DSC), and based on DSC data the glass-reinforced composites (GRC_s) were prepared and characterized by physical and mechanical properties.     

Epoxy resin based on 4,4′-dihydroxydiphenysulfone. I. Synthesis and reaction kinetics with 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone

Epoxy resins based on 4,4′-dihydroxydiphenylsulfone (DGEBS) and diglycidyl ether of bisphenol A (DGEBA) were prepared by alkaline condensation of 4,4′-dihydroxydiphenylsulfone (bisphenol S) with epichlorohydrin and by recrystallization of liquid, commercial bisphenol A-type epoxy resin, respectively. Curing kinetics of the two epoxy compounds with 4,4′-diaminodiphenylmethane (DDM) and with 4,4′-diaminodiphenylsulfone (DDS) as well as T_g values of the cured materials were determined by the DSC method. It was found that the ? SO₂? group both in the epoxy resin and in the harener increases T_g values of the cured materials. DGEBS reacts with the used hardeners faster than does DGEBA and the curing reaction of DGEBS begins at lower temperature than does the curing reaction of DGEBA when the same amine is used. © 1994 John Wiley & Sons, Inc.     

Physicomechanical Properties of Carbon Fiber Reinforced Epoxy Composites

Fabrication of carbon fiber reinforced epoxy composites from the matrix resins diglycidyl ether of bisphenol-A (DGEBA) and tetraglycidyl bis(aminotolyl) cyclohexane (TGBATC) using 4,4′-diaminodiphenyl methane (DDM) as curing agent. The composites were evaluated for their physical and mechanical properties. A significant improvement in the properties was observed on addition of 20 phr of an epoxy fortifier.     

Interactions between silica nanoparticles and an epoxy resin before and during network formation

In polymer nanocomposites, interactions between filler particles and matrix material play a crucial role for their macroscopic properties. Nanocomposites consisting of varying amounts of silica nanoparticles and an epoxy resin based on diglycidyl ether of bisphenol-A (DGEBA) have been studied before and during network formation (curing). Rheology and mainly temperature modulated differential scanning calorimetry (TMDSC) have been used to investigate interactions between the silica nanoparticles and molecules of the epoxy oligomer or molecules of the growing epoxy network. Measurements of the complex specific heat capacity before curing showed that interactions between the nanoparticles and DGEBA molecules are very weak. An expression for an effective specific heat capacity of the silica nanoparticles could be deduced. Examination of the isothermal curing process after addition of an amine hardener yielded evidences for a restricted molecular mobility of the reactants in the cause of network formation. These restrictions could be overcome by increasing the curing temperature. No evidences for an incorporation of the silica nanoparticles into the epoxy network, i.e. for a strong chemical bonding to the network, were found. Interactions between the silica nanoparticles and the epoxy resins under study are assumed to be of a physical nature at all stages of network formation.     

Synthesis and Properties of a Novel Flame-Retardant Epoxy Resin Containing Biphenylyl/Phenyl Phosphonic Moieties

A novel reactive diol, bis-biphenyloxy (4-hydroxy) phenyl phosphine oxide (BBPHPPO) which contains both biphenylyl and phenyl phosphonic groups was synthesized. Flame retardant advanced epoxy resin was obtained by chain extension of diglycidyl ether of bisphenol-A (DGEBA) with the phosphorus-containing diol (BBPHPPO). The thermal properties and flame retardancy of cured epoxy resin were studied. The resulting BBPHPPO containing epoxy system exhibited higher glass transition temperature than that of advanced epoxy resins prepared from bisphenol-A (BA) and tetrabromobisphenol-A (TBBA). The high char yield and the high LOI value were observed to prove the excellent flame retardancy of this phosphorus-containing epoxy resin.     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

Glass fibre reinforced composites of triglycidyl-p-aminophenol

Glass fibre reinforced epoxy composites were fabricated from the matrix resins diglycidyl ether of bisphenol A (DGEBA) and triglycidyl-p-aminophenol (TGAP) using diethylene triamine as curing agent. The epoxy laminates were evaluated for their mechanical properties, dielectrical properties and chemical resistance. Significant improvement in fiexural strength but a slight deterioration in dielectrical properties were observed on incorporation of an epoxy fortifier into the resin system before fabricating the composites.     

Phase separation of poly(ether sulfone imide) modified epoxy resin

Poly(ether sulfone imide)s (PEI) with molecular weight M_n ∼ 10⁴ were synthesized from 3,3′,4,4′-benzophenone tetracarboxylic dianhydride and amine terminated poly(ether sulfone) having molecular weights ranging from M_n ∼ 400 to M_n ∼ 4000. Thus, the PEIs had the same molecular weight but various imide and ether sulfone contents. The PEIs were mixed with a stoichiometric mixture of diglycidyl ether bis-phenol-A (DGEBA)/diamino diphenyl sulfone (DDS). The effect of PEI on the curing reaction of DGEBA/DDS and the morphology of the polymer blend were studied by differential scanning calorimetry (DSC) and optical microscopy. In the DGEBA/DDS/PEI blend with a fixed PEI molecular weight and PEI concentration but with various imide content, the experimental data revealed the PEI with a higher content of ether sulfone had a lower T_g and a better compatibility with solvents and epoxy resins; the curing reaction rate of DGEBA/DDS/PEI was faster for PEI with a higher imide content; the DSC data of cured DGEBA/DDS/PEI showed two T_gs, indicating phase separation between PEI and cured epoxy resins; and the data of optical microscopy showed that the compatibility of PEI with epoxy resins increased with the content of ether sulfone in PEI. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of a high refractive diglycidyl ether of thiodibenzenethiol epoxy resin

High refractive index of epoxy resins used as encapsulant in light-emitting diode (LED) is essential in improving the light extraction efficiency, reducing heat and prolonging the service life of LED packages. In this study, diglycidyl ether of thiodibenzenethiol (DGETDBT), an epoxy resin with high refractive index, was synthesized via a novel method and its chemical structure was characterized with Fourier-transform infrared (FTIR) spectrometer and ¹H NMR spectrometer. Using m-xylylenediamine (MXDA) as curing agent, the curing behavior of DGETDBT was studied by differential scanning calorimetry (DSC) and was compared with that of diglycidyl ether of bisphenol A (DGEBA), a generally used encapsulant in LED. The thermal behavior and optical performance of these two resins were investigated with thermogravimetric analyses, UV?CVis scanning spectrophotometer, and Abbe refractometer, respectively. The results showed that DGETDBT/MXDA resin demonstrated similar curing and thermal behavior to DGEBA/MXDA resin. But its refractive index reaches 1.698, which is significantly higher than that of DGEBA/MXDA resin (1.604). Comparatively, DGETDBT resin can be expected to be a more effective encapsulant of LED.     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal,physical and flame-retardant properties of phosphorus-containing epoxy cured with cyanate ester

Two phosphorus-containing advanced epoxy resins were obtained by chain-extension of diglycidyl ether of bisphenol-A epoxy (DGEBA) resin with 2-(6-oxido-6H-dibenz(c,e)(1,2)-oxaphosphorin-6-yl)-1,4-benzenediol (DOPOBQ), at different stoichiometric ratios. The phosphorus-containing advanced epoxy was separately cured with various dicyanate esters to form flame-retardant epoxy/cyanate ester systems. The effects of phosphorus content and dicyanate ester structure were studied, and compared with those of the control (advanced bisphenol-A epoxy) system. The DOPOBQ-containing epoxy/cyanate ester systems exhibited higher glass transition temperatures, better dimensional stability and better thermal stability.     

Modified Cyclohexanone-Formaldehyde Resin as an Epoxy Resin Curing Agent

Cyclohexanone-formaldehyde (CHF) resin was brominated and the brominated CHF (BCHF) was then reacted with excess aromatic diamines. The aminated CHF resins designated as ACHFs (modified ketone resin) were characterized and then applied as epoxy resin curing agents. Thus, the curing of the commercial epoxy resin diglycidil ether of bisphenol-A (DGEBA) by ACHFs was monitored by differential scanning calorimetric (DSC), based on the the DSC scans, the glass fiber-reinforced composites of DGEBA-ACHF systems were prepared and characterized by chemical resistivity and mechanical properties.     

A comparison of chemorheological models for thermoset cure

A chemorheological study of a thermoset system consisting of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin and a mixture of two armoatic amine curing agents; 4,4′ methylenedianiline (MDA) and m-phenylene diamine (m-PDA), was conducted. Experimentally obtained viscosity data were checked against the predictions of two different viscosity models; one based on a phenomenological equation obtained by modification of the classical Williams–Landel–Ferry (WLF) equation and the other based on an extension of the branching theory originally proposed by Flory. In general, the predictions of both models were in excellent agreement with experimentally obtained isothermal and dynamic viscosity data. The branching theory model was found to have a slight advantage over the phenomenological equation model in describing the viscosity prior to gelation in a fast heating cure cycle.     

Effect of sulfur in different valence on flame retardance of epoxy resin for light emitting diode

A novel phosphorus/nitrogen-containing flame retardant (DOPO-AM) was synthesized by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and acrylamide (AM) and its chemical structure was characterized. DOPO-AM was added into diglycidyl ether of bisphenol-A (DGEBA) with curing agent m-xylylenediamine (MXDA)to prepare flame retarded epoxy resin to reduce the possibility of fire. The compounds with different valences sulfur respectively replace partial DGEBA resin to study the effects of sulfur valences on the flame retardance of epoxy resins. The results indicated that DOPO-AM had excellent flame retardance for epoxy resin. When phosphorus content was only 0.75%, DGEBS resin containing DOPO-AM achieved the limiting oxygen index value of 34.55% and vertical burning test (UL-94) V-0 rating. Although sulfur element is help for refractive index of epoxy resin, sulfur element in three kinds of valences all weaken the flame retardant of epoxy resin. Improving phosphorus content is help for the synergistic effect of P N and P N S. Moreover, the flame retardance is not proportional to sulfur valence, sulfide with +2 valence had the best flame retardance. However, +6 valence sulfonic with strong oxidation effect worsen the flame retardant. Simultaneous thermal analysis of thermogravimetric analyzer and differential scanning calorimeter and scanning electronic microscopy photographs verified the above conclusion.     

Curing of DGEBA epoxy resin by low generation amino‐group‐terminated dendrimers

Low generation amino‐group‐terminated poly(ester‐amine) dendrimers PEA1.0 (NH₂)₃ and PEA1.5 (NH₂)₈, and poly(amido‐amine) dendrimer PAMAM1.0 (NH₂)₄ were used as diglycidyl ether of bisphenol A (DGEBA) epoxy resin hardeners. Thermal behavior and curing kinetics of dendrimer/DGEBA systems were investigated by means of differential scanning calorimetry (DSC). Compared with ethylene diamine (EDA)/DGEBA system, the dendrimer/DGEBA systems gradually liberated heat in two stages during the curing process, and the total heat liberated was less. Apparent activation energy and curing reaction rate constants for dendrimer and EDA/DGEBA systems were estimated. Thermal stabilities and mechanical properties of cured thermosetting systems were examined as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3902–3906, 2006