Mass spectral studies of some epoxy resin precursors

The mass spectra were determined of three epoxy resin precursors: N,N-bis-(2,3-epoxypropyl)-N′,N′-dimethyl-4,4′-diaminodiphenylenemethane (G2A); N,N′-bis-(2,3-epoxypropyl)-N,N′-dimethyl-4,4′-diaminodiphenylene methane (G2S); and N′,N′,N′,N′-tetrakis-(2,3-epoxypropyl)-4,4′-diaminodiphenylene methane (TGDDM); and of three related model compounds: N,N-dimethylaniline (DMA); N-methyl-N-glycidylaniline (MGA) and N,N-digrycidylaniline (DGA). The results helped to confirm the structure of the resin precursors and are intended to pave the way for subsequent thermal degradation studies of cured resin samples. Despite the similarity in chemical structure of the compounds studied there are quite large differences in the mass spectral results obtained.     

Structure and Properties Relationships of Epoxy Resins Part 1: Crosslink Density of Cured Resin: (II) Model Networks Properties

Carefully designed resin precursors of high purity, viz. N,N-bis-(2,3-epoxypropyl)-N',N-dimethyl-4,4′-diaminodiphenylenemethane (G2A) and N,N-bis-(2,3-epoxypropyl)-N,N-dimethyl-4,4′-diamino-diphenylenemethane (G2S) were used in combination with N,N,N',N-tetrakis-(2,3-epoxypropyl)-4,4′-diaminodiphenylene methane, TGDDM, and cured with stoichiometric amounts of 4,4′-diamino-diphenylene methane (DDM) to produce networks with a range of controlled crosslink density. The tensile moduli E of the networks in the rubbery state, at T_g+30°C, T_g+45°C and T_g+60°C, were measured using a thermal mechanical analyser. Using the statistical theory of rubber elasticity and the observed values of E, the number average molecular weights between crosslink points M_c for the cured resins were deduced. The experimental M_c values were then compared with those derived by calculations based on a probabilistic model of the network proposed by Chu and Seferis.¹ The experimental M_c values were 2.5 to 5.5 times larger than the calculated ones. The differences were attributable to a consumption of only 40% of the available secondary amino hydrogen via epoxy-amine reaction. A direct relationship was established between the glass transition temperature and the crosslink density 1/M_c for the resins, and the dynamic mechanical properties were studied. The thermal stability of cured resins studied by thermo-gravimetric analysis indicated an enhancement of stability as 1/M_c was reduced. The amount of water absorbed by cured resin was directly proportional to 1/M_c.     

Epoxy resins based on aromatic glycidylamines. V. Shelf life of TGDDM-based epoxy resins

The effect of aging on resin composition was investigated as a part of a study concerned with the evaluation of epoxies containing N, N, N′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM). Long-term stability of three different epoxy resins based on TGDDM and their mixtures with 4,4′-diaminodiphenylsulfone (DDS) was followed at 23 ± 2°C at a relative humidity ranging from 45% to 55%, by means of GPC and HPLC; short-term stability of the resins was evaluated at 125°C.     

Fibre reinforced composites of multifunctional epoxy resins

Glass and carbon fibre reinforced epoxy composites were fabricated for N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenyl methane (TGDDM) and its formulated systems with tri- and di-functional reactive epoxy diluents using 30% diaminodiphenyl sulphone (DDS) as a curing agent. The epoxy laminates were evaluated for their physical, chemical and mechanical properties [at room (26°C) and high (100°C) temperatures]. A marginal increase (<20%) in the mechanical properties of CFRP was found compared with GFRP laminates. Incorporation of epoxy diluents altered the mechanical properties of the composites significantly. The incorporation of triglycidyl-4-aminophenol diluent to TGDDM systems resulted in an improvement in mechanical properties of about 2–6%.     

Epoxy systems with improved water resistance,and the non-fickian behaviour of epoxy systems during water ageing

N,N-Bis (2, 3-epoxypropyl) aniline and 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl) aniline] containing bromo, chloro, trifluoromethyl or polyfluoroalkoxy substituents were synthesised and cured with aromatic diamines in order to investigate the effect of substituted halogen on water absorption. Significant improvements were achieved: thus use of 4,4′-methylenebis-[N, N-bis (2, 3-epoxypropyl)-3, 5-dichloroaniline] and 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl)-3-(trifluoromethyl) aniline] instead of 4,4′-methylenebis-[N,N-bis (2,3-epoxypropyl) aniline] reduced the water absorption by about a half. Departures from Fickian behaviour were observed during water immersion ageing at room temperature and were a general feature of the epoxy systems examined. Plots of water absorption against the Fickian parameter (√t/d) usually showed at least mild sigmoid character and were not independent of specimen thickness. Further, slow continued uptake of water occurred during long-term ageing, and evidence is provided that the associated network distortions are reversible.     

Cure kinetics of multifunctional epoxies with 2,2′‐dichloro‐4,4′‐diaminodiphenylmethane as hardener

The curing behavior of the epoxy resin N,N,N′,N′‐tetraglycidyldiaminodiphenyl methane (TGDDM) with triglycidyl p‐aminophenol as a reactive diluent was investigated using 2,2′‐dichloro‐4,4′‐diaminodiphenylmethane (DCDDM) as the curing agent. The effect of the curing agent on the kinetics of curing, shelf‐life, and thermal stability in comparison with a TGDDM‐diaminodiphenylsulfone (DDS) system was studied. The results showed a lesser activation energy at the lower level of conversion with a broader cure exotherm for the epoxy‐DCDDM system in comparison with the epoxy‐DDS system, although the overall activation energy for the two systems was comparable. TGA studies showed more stability in the epoxy‐DCDDM system than in the epoxy‐DDS system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2097–2103, 2000     

Characterization of the cure of TGDDM/DDS epoxy resins by chemiluminescence I. Spectral and thermal analysis

The emission of weak visible chemiluminescence (CL) during the cure of a tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM)-based epoxy resin, with three different concentrations of 4,4′-diaminodiphenylsulfone (DDS) has been studied at 135°C. Spectral analysis indicates that the CL originates from trace oxidation of the TGDDM resin and the emission intensity is sensitive to the viscosity changes during cure. From thermal analysis data, sharp discontinuities in CL intensity are shown to occur at the gel point. The temperature dependence of CL from a cured resin also shows a sharp discontinuity at T_g. These results indicate that CL provides a sensitive monitor of both the kinetics of gelation and the network formation in this epoxy resin.     

Glass fiber-reinforced epoxy composites

Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethane

1 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane.

(TGDDM) and tetraglycidyl bis(o-toluidino)-methane

2 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane.

(TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.     

Effects of Fortifier on Glass/Carbon Fiber Reinforced Tetrafunotional Epoxy Resin

Glass fiber reinforced epoxy composites were prepared using tetra-N-glycidyl-p,p′-diaminodiphenyl methane (TGDDM) as a resin matrix with/without fortifier PGEHA/VCDRC (at 20 phr level) using DDM/DDS as curing agent; the composites were evaluated for their various physical, mechanical, chemical, and electrical properties. Carbon fiber (i.e., unidirectional, bidirectional, and chopped) reinforced composites of TGDDM with/without epoxy fortifier PGEHA/VCDRC (at 20 phr level) were also prepared and evaluated for their physical and some mechanical and chemical properties. It is observed that incorporation of fortifier (at 20 phr level) improves these properties significantly.     

Phosphorus‐containing epoxy resins: Thermal characterization

Three novel aromatic phosphorylated diamines, i.e., bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl} pyromellitamic acid (AP), 4,4′‐oxo bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AB) and 4,4′‐hexafluoroisopropylidene‐bis N,N′‐{3‐[(3‐aminophenyl)methyl phosphinoyl] phenyl}phthalamic acid (AF) were synthesized and characterized. These amines were prepared by solution condensation reaction of bis(3‐aminophenyl)methyl phosphine oxide (BAP) with 1,2,4,5‐benzenetetracarboxylic acid anhydride (P)/3,3′,4,4′‐benzophenonetetracarboxylic acid dianhydride (B)/4,4′‐(hexafluoroisopropylidene)diphthalic acid anhydride (F), respectively. The structural characterization of amines was done by elemental analysis, DSC, TGA, ¹H‐NMR, ¹³C‐NMR and FTIR. Amine equivalent weight was determined by the acetylation method. Curing of DGEBA in the presence of phosphorylated amines was studied by DSC and curing exotherm was in the temperature range of 195–267°C, whereas with conventional amine 4,4′‐diamino diphenyl sulphone (D) a broad exotherm in temperature range of 180–310°C was observed. Curing of DGEBA with a mixture of phosphorylated amines and D, resulted in a decrease in characteristic curing temperatures. The effect of phosphorus content on the char residue and thermal stability of epoxy resin cured isothermally in the presence of these amines was evaluated in nitrogen atmosphere. Char residue increased significantly with an increase in the phosphorus content of epoxy network. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2235–2242, 2002     

Cure monitoring of aerospace epoxy resins and prepregs by Fourier transform infrared emission spectroscopy

Spectral analysis of the infrared radiation emitted from thin films of resin transferred from the surface of high performance aerospace carbon fibreepoxy composite prepregs and heated to the cure temperature allows the cure chemistry and kinetics to be monitored in real time. Quantitative spectra with excellent signal-to-noise ratio are obtained by heating a thin resin film on a platinum hotplate fitted to the external optics of a Fourier transform infrared (FTIR) spectrometer and referencing the resulting emission (with the platinum emission subtracted) to a graphite black body at the same temperature. The resulting spectra are identical to absorption spectra and the quantitative features of the analysis are demonstrated by the appearance of isosbestic points during the curing reactions, so indicating that concentration profiles of the reacting species may be obtained. From the initial rate of amine and epoxy consumption, activation energies of 75kJ mol⁻¹ were obtained for both functional groups in the uncatalysed resin 4,4′-tetraglycidyl diamino diphenyl methane (TGDDM) with 27% 4,4′-diaminodiphenylsulfone (DDS), while values of 74 and 89kJ mol⁻¹ were obtained for amine and epoxy consumption from the TGDDM/DDS prepreg catalysed with boron trifluoride monoethylamine (Hercules 3501–6), consistent with homopolymerization occurring in the prepreg as well as amine–epoxy addition. Analysis of the FTIR emission at 177°C of resin from prepreg aged up to 90h at 23°C and 55% relative humidity shows a lowering of epoxy and amine concentration and a higher rate of cure, consistent with the formation of catalytic species. This technique may be used to monitor changes in surface properties such as tack and resin transfer, in addition to changes in the cure profile of the aged epoxy propreg.     

Use of the frequency dependence of the impedance to monitor viscosity during cure

The ability to conveniently and continuously measure the processing properties of polymer resins is important both to the resin supplier and to the fabricator. Frequency dependent electromagnetic sensors (FDEMS) provide an in-situ technique for continuous measurement of the resin's rheological changes both in a laboratory press and in manufacturing tools in an autoclave. In this paper the frequency dependence of ?*(w) is used to quantitatively monitor the viscosity for a tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) amine epoxy, to quantitatively monitor the viscosity during processing In a styrene-polyester resin, and to monitor the cure process in an autoclave during cure of a high temperature polyimide-graphite prepreg. In addition, the technique is used to measure the viscosity at various ply positions in a thick TGDDM graphite epoxy laminate during processing in an autoclave.     

Multifunctional epoxy resins

The curing behavior of epoxy resins prepared by reacting epichlorohydrin with 4,4′-diaminodiphenyl methane (DADPM)/4,4′-diaminodiphenyl ether (DADPE) or 4,4′-diaminodiphenyl sulfone (DDS) was investigated using DDS and tris-(m-aminophenyl)phosphine oxide (TAP) as curing agents. A broad exothermic transition with two maxima were observed in the temperature range of 100–315°C when TAP was used as the curing agent. The effect of varying DDS concentration on curing behavior of epoxy resin was also investigated. Peak exotherm temperature (T_exo) decreased with increasing concentration of DDS, whereas heat of curing (ΔH) increased with an increase in amine concentration up to an optimum value and then decreased. Thermal stability of the resins, cured isothermally at 200°C for 3 h, was investigated using thermogravimetric analysis in a nitrogen atmosphere. Glass fiber-reinforced multifunctional epoxy resin laminates were fabricated and the mechanical properties were evaluated. © 1993 John Wiley & Sons, Inc.     

Curing behavior,thermal, and mechanical properties of epoxy resins cured with a novel liquid crystalline dicarboxylic acid curing agent

A novel di‐carboxylic acid curing agent (DACA) was successfully synthesized and cured with three different epoxy resins: glycidyl end‐capped poly(bisphenol‐A‐co‐epichlorohydrin) (pDGEBA, M_n = 377), N,N‐diglycidyl‐4‐glycidyloxyaniline (TGAP), and 4,4′‐methylenebis(N,N‐diglycidylaniline) (TGDDM). The cured epoxy exhibited excellent thermal stability, which was indicated by high initial degradation temperature (T_id) and char yield. The T_id values of cured epoxy were in the range of 327–338°C, and the char yields increased with increasing epoxy functionality. The char yields of cured DACA/pDGEPA, DACA/TGAP, and DACA/TGDDM samples were 21.1, 60.4, and 66.9%, respectively. In addition, the cured epoxy samples also showed low coefficients of thermal expansion and high storage moduli (E′), which were around 60 ppm/°C and 2800 MPa, respectively. The failure surfaces were ductile and rough, so the cured epoxy samples are expected to have high fracture toughness and impact strength. POLYM. ENG. SCI., 54:695–703, 2014. © 2013 Society of Plastics Engineers     

Curing kinetics and thermal properties of diglycidylether of bisphenol A with various diamines

To prepare a high‐performance epoxy, we synthesized three types of diamines {N,N′‐(4,4′‐diphenylether)‐bis(4‐aminophthalimide), 4,4′‐bis(p‐aminophenoxy)dibenzalphentaerythriol, and 2,2′‐bis[4‐(p‐aminobenzoyl)phenyl]propane} as epoxy curing agents with a two‐step reaction sequence. The structures of the synthesized diamines were confirmed with Fourier transform infrared and nuclear magnetic resonance spectroscopy. The curing kinetics and thermal stability of the cured epoxy resin with diglycidylether of bisphenol A were estimated with differential scanning calorimetry and thermogravimetric analysis under a nitrogen atmosphere. The kinetics parameters were determined with the Ozawa and Kissinger equations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 279–284, 2001     

Epoxy resin cure. II. FTIR analysis

Fourier transform infrared (FTIR) spectroscopy is used to determine the cure rate of an epoxy resin consisting of Tetraglycidyl-4,4′-diaminodiphenyl methane (TGDDM) and diaminodiphenylsulfone (DDS). Cure rates at 120 and 160°C are shown to increase noticeably when 1% BF₃–MEA is added to either TGDDM to TGDDM plus DDS. Fluoroboric acid is shown to increase the cure rates even more than the BF₃–MEA. These Results combined with the NMR results in the accompanying article indicate that BF₃–MEA is not a catalyst for epoxy resin cure. Instead it is rapidly hydrolyzed to fluoroboric acid which acts as the catalyst.     

New tetrafunctional epoxy resin system with increased shelf life

Chlorine‐ and methyl‐substituted aromatic diamines based on diaminodiphenylmethane were epoxidized and characterized. The effect of different substituents on epoxidation was studied. The cure studies of the two new tetrafunctional resins in comparison with unsubstituted resin N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) was carried out by DSC with 3,3′‐dichloro‐4,4′diaminodiphenylmethane (o‐DCDDM; 30% w/w) as a common curing agent. The mechanical properties such as flexural, Izod impact, heat distortion temperature (HDT), of such cured neat resins were also studied. The results of the cure studies indicate that the substitution of the α‐hydrogen of the resin by chlorine or methyl group decreases the reactivity of the resin leading to an increase in the shelf life. This study also indicates that the functionality of the resin plays a pivotal role in the reactivity and thus the shelf life of an epoxy resin system. The results of the mechanical properties of the neat resin casts obtained by subjecting to a common cure schedule when compared with the unsubstituted resin showed a decrease in impact strength, which is obvious because of the presence of a bulky pendant group but the impact strength was higher than that of the TGOS30 resin system. Results of flexural strength of the different substituted neat resin casts did not show much of a deviation from that of the unsubstituted resin system. The HDT results indicate no significant difference in the values of the unsubstituted resin vis‐a‐vis with substituted resin systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2790–2801, 2004     

Interaction and properties of epoxy‐amine system modified with poly(phthalazinone ether nitrile ketone)

An epoxy based on the tetraglycidyl 4,4′‐diaminodiphenyl‐ methane (TGDDM)/bisphenol A type novolac(F‐51) cured with 4,4′‐diaminidiphenysulfone (DDS) has been modified with Poly (phthalazinone ether nitrile ketone)(PPENK). The interaction between the PPENK and epoxy resin have been investigated by differential scanning calorimetry (DSC), FT‐IR, and dynamic mechanical analysis (DMA). The thermal and mechanical properties were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), flexural, impact strength, and the critical stress intensity factor tests. The results showed that a large number of physical crosslinks formed by intermolecular and intramolecular hydrogen bonding indeed existed in the TGDDM/F‐51/PPENK blends. These interactions gave good compatibility between PPENK and epoxy resin. So that any phase separation had not been detected by DMA and scanning electron microscope (SEM). Beyond that the interaction could also be a benefit to the thermal and mechanical properties. Compared with the neat epoxy resin, the critical stress intensity factor values reached the maximum at 10‐phr PPENK, as well as the impact strength. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42938.     

Tertiary‐amine‐free,non‐planar,sulfone‐containing,tetrafunctional epoxy and its application as a high temperature matrix

Non‐amine‐derived tetrafunctional epoxies have several advantages over the amine‐derived N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenyl methane (TGDDM) in high temperature applications. Although two non‐amine‐derived tetrafunctional epoxies were developed in our laboratory, further improvements in toughness using less loading amount is still desirable. Thus, a tertiary‐amine‐free, non‐planar and triphenylmethane‐containing tetrafunctional epoxy (STFE) with a sulfone spacer was synthesized. When it was mixed with diglycidyl ether of bisphenol A (DGEBA) and cured with 4,4′‐diaminodiphenylsulfone (DDS), both thermal and mechanical performances outperformed TGDDM. Moreover, STFE modified system shows the highest toughness (35.7 kJ m^–2) among three amine‐free and triphenylmethane‐containing epoxies at merely 5 wt% loading. Molecular simulation and thermomechanical analysis results suggest that the improved mechanical properties could be related to the geometry of the molecule and larger free volume. Despite a marginal drop in T_g, the thermal degradation temperature is better than that of TGDDM/DDS. In addition, the moisture resistance of STFE/DGEBA/DDS is much better than that of TGDDM/DDS. Thus, STFE modified DGEBA could be a potential replacement for TGDDM in some high temperature applications. © 2020 Society of Chemical Industry     

Studies on the curing kinetics and thermal stability of the novel tetrafunctional epoxy resin N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline

A novel tetrafunctional epoxy resin, namely N,N,N′N′-tetrakis(2,3-epoxypropyl)-4,4′-(1,4-phenylenedioxy)dianiline, has been synthesized. The curing kinetics has been studied by differential scanning calorimetry (DSC) using various amine curing agents. Thermal stabilities of the cured products have been investigated by thermogravimetric (TG) analyses. The overall activation energies for the curing reactions are observed to be in the range 63.6–196.7 kJ·mol^–1. The cured products have good thermal stability.