脲衍生物对环氧树脂/双氰双胺固化体系潜伏性促进作用研究

本文用DSC、TBA、旋转粘度计等手段对一系列不同结构及不同取代基取代的脲衍生物对环氧树脂/双氰双胺固化体系的潜伏性促进作用作了考察。结果表明,其促进效果随脲的α位取代烷基碳原子数增加而减弱,而其β、γ位上的取代基团变换时对促进作用无明显影响。由此得出4,4-二(N,N-二甲基)脲二苯甲烷(简称M-二甲)和2,4-二(N,N-二甲基)脲甲苯(简称T-二甲)二种脲衍生物在本丈所考察的28种化合物中具有最显著的促进效果,其中T-二甲的促进活性略高于M-二甲,它们均可使上述固化体系的固化温度降至130℃左右,含有此促进剂的固化体系即使在30℃下贮存,其粘度保持基本不变的时间仍可达三个月以上。     

Cationic cure kinetics of a polyoxometalate loaded epoxy nanocomposite

The reaction cure kinetics of a novel polyoxometalate (POM) loaded epoxy nanocomposite is described. The POM is dispersed in the epoxy resin up to volume fractions of 0.1. Differential scanning calorimetry measurements show the cure of the epoxy resin to be sensitive to the POM loading. A kinetics study of the cure exotherm confirms that POM acts as a catalyst promoting cationic homopolymerization of the epoxy resin. The cure reaction is shown to propagate through two cure regimes. A fast cure at short time is shown to be propagation by the activated chain end (ACE) mechanism. A slow cure at long time is shown to be propagation by the activated monomer (AM) mechanism. The activation energies for the fast and slow cure regimes agree well with other epoxy based systems that have been confirmed to propagate by the ACE and AM mechanisms.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Miscibility and cure kinetics studies on blends of bisphenol-A polycarbonate and tetraglycidyl-4,4′-diaminodiphenylmethane epoxy cured with an amine

Differential scanning calorimetry (DSC) has been applied to characterize the glass transition behavior of the blends formed by bisphenol-A polycarbonate (PC) with a tetrafunctional epoxy (tetraglycidyl-4,4′-diaminodiphenyl methane, TGDDM) cured with 4,4′-diaminodiphenylsulphone (DDS). A rare miscibility in the complete composition range has been demonstrated in these blends. Additionally, the blend morphology was examined using scanning electron microscopy (SEM) and a homogeneous single-phase PC/epoxy network has been observed in the blends of all compositions. Moreover, polycarbonate incorporation has been found to exert a distinct effect on the cure behavior of the epoxy blends. The cure reaction rates for the epoxy-PC blends were significantly higher due to the presence of PC. In addition, the cure mechanism of the epoxy blends was no longer autocatalytic. An n-th order reaction mechanism with n = 1.2 to 1.5 has been observed for the blends of DDS-cured epoxy with PC of various compositions studied using DSC. The proposed n-th order kinetic model has been found to describe well the cure behavior of the epoxy/PC blends up to the vitrification point. © 1995 John Wiley & Sons, Inc.     

环氧交联网T_g转变的tanδ-T曲线解析

本文系统地研完了预聚物分子量、固化剂配比和固化条件对环氧交联网T_g松弛内耗峰松弛时间分布的影响。本实验和理论研究结果首次证明了环氧交联网T_g松弛过程具有单一松弛时间描述的线性标准固体的特征,与预聚体分子量、固化剂配比和固化条件无关。此结果可用环氧交联网的两相结构特征加以解释。     

环氧交联网Tg转变的tanδ-T曲线解析

 本文系统地研完了预聚物分子量、固化剂配比和固化条件对环氧交联网T_g松弛内耗峰松弛时间分布的影响。本实验和理论研究结果首次证明了环氧交联网T_g松弛过程具有单一松弛时间描述的线性标准固体的特征,与预聚体分子量、固化剂配比和固化条件无关。此结果可用环氧交联网的两相结构特征加以解释。     

Curing kinetics of liquid-crystalline epoxy resins

By endcapping mesogenic rigid rod molecules with reactive epoxy groups a novel class of liquid-crystalline thermoset has been obtained. In fact is has been shown that the nematic molecular arrangement is sustained over the crosslinking reaction of liquid-crystalline epoxy resins when the curing reaction is carried out in the thermal stability range of the liquid-crystalline phase. Calorimetric analysis was used in characterizing the isothermal cure. An unsophisticated model is proposed for evaluating the activation energies of the crosslinking reaction. For liquid-crystalline epoxy resins lower activation energies result with respect to the cure reactions for non liquid-crystalline epoxy resins.     

Cure process and reaction-induced phase separation in a diepoxy–diamine/PMMA blend. Monitoring by steady-state fluorescence and FT-IR (near and medium range)

Poly(methyl methacrylate), PMMA, was chosen as an additive for an epoxy system based on the cured product of (a) diglycidyl ether of bisphenol A labeled with 5-dimethylaminonaphthalene-1-(2-aminoethyl) sulfonamide and (b) 1,5-diamino-2-methylpentane. Fourier transformed infrared spectroscopy (near, FT-NIR, and medium, FT-MIR, ranges) and steady-state fluorescence spectroscopy were used to monitor the epoxy cure reaction and the induced phase separation. The PMMA seems to exert a change in the mechanism of the epoxy cure reaction by means of a slight enhancement of the secondary amino group reactivity. It has been demonstrated that following the fluorescence response of the dansyl chromophore chemically bonded to the epoxy component is a way to monitor the cure process in a general sense, not only accounting for the chemical changes but also being additionally possible to detect the reaction-induced phase separation at a molecular scale. The fluorescence results, in terms of the first moment of the emission band, point out that the dilution effect is affecting the physicochemical changes of the modified epoxy system quite more exclusively than the chemical changes. Finally, a semiempirical model to explain the behavior of the dansyl fluorescence during the curing of a PMMA/diepoxy–diamine blend showing a reaction-induced phase separation has been proposed. The proposed model allows estimating the composition of the phases after nearly complete cure.     

Epoxy resins and epoxy blends studied by near infra-red spectroscopy

The cure and the final network of epoxy resins have been investigated by numerous techniques, nevertheless a clear understanding of this network structure has not yet been achieved. FTIR analysis of polymeric materials provides highly precise measurements that are widely interpretable in terms of chemical structure. Yet the high absorption of fundamental bands requires careful sample preparation to reduce the thickness of the sample or special reflection techniques are needed. Furthermore, the occurrence of overlapping bands for epoxy resin (N-H and O-H vibrations in the 3000 cm⁻¹ region) renders the quantitative analysis in the region mid IR particularly difficult. However, the overtone and combination bands are 10–100 times weaker than the fundamental ones and are observed in near infrared (NIR) region. Longer pathlengths than Mid IR ones can be used allowing transmission analysis of thick samples (1-20 mm) without special preparation. NIR absorption bands have different intensities depending on the anharmonicity of vibrations. The strongest absorption bands are due to protons connected to carbon, nitrogen, oxygen. Hydrogen bonding due to inter- and intramolecular interactions can cause band broadening, peak position shifts and intensity variations. NIR spectroscopy is therefore a useful technique to investigate polymeric materials and was used to study the cure reactions of various epoxy resins cured with amine hardener. Using different NIR techniques (reflectance, transmission and microscopy) we will briefly present some results concerning hydrogen bonding between epoxy and amine hardener before curing, epoxy resins, glass/epoxy composites and epoxy/PES (polyethersulfone) blends.     

Influence of accelerator type on properties of NR/EPDM blends

The effect of accelerator type on processability and mechanical properties of 60/40 natural rubber/ethylene propylene diene monomer (NR/EPDM) blend was investigated. Three groups of commercial accelerators were selected, i.e., sulfenamide group (Santocure-TBBS), thiuram group (Perkacit-TMTD) and mercapto group (Perkacit-MBT and Perkacit-MBTS). The results reveal that the accelerator type not only affects the cure characteristics, but also has great influence on compound viscosity. Among the accelerators studied, TBBS gives the best processing safety together with a relatively high state of cure. In addition, TBBS also provides good cure compatibility between the NR and EPDM phases, giving rise to superior mechanical properties. Although TMTD could give a high state of cure, it causes severe cure incompatibility, leading to poor tensile strength. Due to their lower reactivity, the two mercapto accelerators give a relatively low state of cure. Therefore, the vulcanizates obtained possess low modulus and hardness as well as degree of elasticity. Surprisingly, it is found that the tensile strength of the MBTS-cured blend is relatively high. Good cure compatibility given by MBTS could be used to explain the results.     

A systematic study of the microwave and thermal cure kinetics of the DGEBA/DDS and DGEBA/DDM epoxy‐amine resin systems

The microwave and thermal cure processes for the epoxy-amine systems (epoxy resin diglycidyl ether of bisphenol A, DGEBA) with 4,4′-diaminodiphenyl sulphone (DDS) and 4,4′-diaminodiphenyl methane (DDM) have been investigated for 1 : 1 stoichiometries by using fiber-optic FT-NIR spectroscopy. The DGEBA used was in the form of Ciba-Geigy GY260 resin. The DDM system was studied at a single cure temperature of 373 K and a single stoichiometry of 20.94 wt% and the DDS system was studied at a stoichiometry of 24.9 wt% and a range of temperatures between 393 and 443 K. The best values of the kinetic rate parameters for the consumption of amines have been determined by a least squares curve fit to a model for epoxy/amine cure. The activation energies for the polymerization of the DGEBA/DDS system were determined for both cure processes and found to be 66 and 69 kJ mol⁻¹ for the microwave and thermal cure processes, respectively. No evidence was found for any specific effect of the microwave radiation on the rate parameters, and the systems were both found to be characterized by a negative substitution effect. Copyright © 2002 John Wiley & Sons, Ltd.     

Kinetics and mechanistic investigation of epoxy–anhydride compositions cured with quaternary phosphonium salts as accelerators

Mechanism and curing kinetics of bisphenol A epoxy resin–iso‐methyltetrahydrophthalic anhydride compositions using quaternary phosphonium salts as accelerators were investigated by differential scanning calorimetry (DSC) and electrospray mass‐spectrometry (ESI‐MS). The DSC method was applied to investigate curing kinetics and apparent activation energy values for the overall curing process. The DSC results showed that some of the phosphonium salts lead to a lower activation energy, that means they are more effective accelerators for the curing of epoxy–anhydride systems. The mechanism of curing was studied by ESI‐MS using the model reaction of epichlorohydrin (E) with phthalic anhydride (PA) in the presence of phosphonium salts or 2‐methylimidazole. Products containing the alkyl moiety of the phosphonium salt in form of alkyl esters could be identified. This suggests that the phosphonium salts activate the anhydride by electrophilic attack. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1088–1097     

Evolution of structure and properties of a liquid crystalline epoxy during curing

The evolution of structure, and thermal and dynamic mechanical properties of a liquid crystalline epoxy during curing has been studied with differential scanning calorimetry (DSC), polarized optical microscopy, x-ray scattering, and dynamic mechanical analysis. The liquid crystalline epoxy was the diglycidyl ether of 4,4′-dihydroxy-α-methylstilbene (DGEDHMS). Two curing agents were used in this study: a di-functional amine, the aniline adduct of DGEDHMS, and a tetra-functional sulfonamido amine, sulfanilamide. The effects of curing agent, cure time, and cure temperature have been investigated. Isothermal curing of the liquid crystalline epoxy with the di-functional amine and the tetra-functional sulfonamido amine causes an increase in the mesophase stability of the liquid crystalline epoxy resin. The curing also leads to various liquid crystalline textures, depending on the curing agent and cure temperature. These textures coarsen during the isothermal curing. Moreover, curing with both curing agents results in a layered structure with mesogenic units aligned perpendicular to the layer surfaces. The layer thickness decreases with cure temperature for the systems cured with the tetra-functional curing agent. The glass transition temperature of the cured networks rises with increasing cure temperature due to the increased crosslink density. The shear modulus of the cured networks shows a strong temperature dependence. However, it does not change appreciably with cure temperature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2363–2378, 1997     

Investigation of cure kinetics of epoxy resin/organic montmorillonite system by differential scanning calorimetry

The cure kinetics of the epoxy resin (EP)/organic montmorillonite, with 4-diamino diphenyl methane (DDM) as curing agent, was studied by non-isothermal differential scanning calorimetry (DSC) at four linearly programmed heating rates of 5, 10, 15, and 20 deg/min, and the effects of original montmorillonite (OMMT) on cure kinetics of epoxy resin were investigated. A two parameter (m, n) autocatalytic model was used to describe the cure kinetics of the epoxy resins. The kinetic parameters were calculated with the Malek method and the curves obtained by the Málek method showed a good agreement with experimental data for EP/DDM and EP/DDM/OMMT systems. The results, based on the isoconversional method showed that the activation energy was obvious difference with the addition of OMMT in the early stages of the cure, which indicated that the OMMT have catalytic effect on the epoxy ring-opening.     

Evaluation of furfurylamines as curing agents for epoxy resins

Epoxy resin adhesives are widely used because of their strength, versatility, and ability to bond a variety of substrates. Furfurylamines represent a potential, new class of epoxy curing agents. Furfuryl amine (FA), tetrahydrofurfuryl amine (THFA), and 5,5′-methylenebis-2-furanmethanamine (DFA) were studied as possible epoxy curing agents. The utility of FA and THFA are limited by their volatility at the temperatures needed to effect cure of diglycidyl-ether of bisphenol A (DGEBA) based epoxy resins. DFA is a very effective epoxy curing agent with the ability to cure DGEBA at rates similar to that of standard epoxy curing agents such as liethylenetriamine.     

In situ thermoset molecular composites

The polymerization of rigid rod polymer precursors in a reactive matrix precursor, which is later cured in the mold, constitutes the in situ process. A poly-azomethine (PAM) was used as the rigid rod molecule. The resin used was an epoxy. We discuss the prediction of mechanical properties using micromechanics equations for chopped fiber composites. The chemistry used to synthesize the rigid rod polymer PAM in the epoxy precursor is reviewed. Approaches to better control the cure of these epoxy systems through cure kinetics and cure rheology studies completes the thermoset in situ molecular composite process. There was a 71% increase in tensile modulus in comparison to that of the neat epoxy resin. Molecular modeling simulations and continuum mechanics are used to help understand these findings. PAM/epoxy systems were used as a matrix material in the fabrication of unidirectional glass fiber/(PAM/epoxy) structural composites. © 1994 John Wiley & Sons, Inc.     

High melting thermoplastic/epoxy resin blends: Influence of the curing reaction on the crystallization and melting behavior

The influence of the cure process and the resulting reaction‐induced phase separation (RIPS) on the crystallization and melting behavior of polyoxymethylene (POM) in epoxy resin diglycidylether of bisphenol A (DGEBA) blends has been studied at different cure temperatures (180 and 145 °C). The crystallization and melting behavior of POM was studied with DSC and the simultaneous blend morphology changes were studied using OM. At first, the influence of the epoxy monomer on the dynamically crystallized POM was investigated. Secondly, a cure temperature above the melting point of POM (T_cure = 180 °C) was applied for blends with curing agent to study the influence of resulting phase morphology types on the crystallization behavior of POM in the epoxy blends. Large differences between particle/matrix and phase‐inverted structures have been observed. Thirdly, the cure temperature was lowered below the melting temperature of POM, inducing isothermal crystallization prior to RIPS. As a consequence, a distinction was made between dynamically and isothermally crystallized POM. Concerning the dynamically crystallized material, a clear difference could be made between the material crystallized in the homogeneous sample and that crystallized in the phase‐separated structures. The isothermally crystallized POM was to a large extent influenced by the conversion degree of the epoxy resin. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2456–2469, 2007     

Study on curing reaction of epoxy resin modified with prepolymers containing spiro orthocarbonate

Prepolymers were prepared by the reaction of 3,9-dihydroxyethyl-3′9′-dibenzyl-1,5,7,11-tetraoxaspiro(5,5)undecane with 4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexa-methylene diisocyanate (HDI). The number-average molecular weights of the prepolymers can be controlled by changing the mole ratios of spiro compound and diisocyanates. Kinetic studies of the cure reaction for the epoxy resin system modified with or without prepolymers were followed by a HLX-1 dynamic torsional vibration apparatus. The results indicated that gel time (t_g) and activation energy (E_a) increased as the content of prepolymers in the epoxy resin system increased. A difference with the cure reaction of the pure epoxy resin, the second-order reaction for the epoxy resin modified with the prepolymers, was obtained. Rate constants (k) of the cure reaction are 0.231 min^?1 for the epoxy resin, and 0.312 min^?1 for the modified epoxy resin. The mechanism of the cure reaction was discussed. © 1995 John Wiley & Sons, Inc.     

Study of the effect of accelerators on the curing rate of epoxy systems

The effect exerted by accelerators in curing of NPER 128 epoxy resin on the formation kinetics and properties of the final product was determined.     

Effect of Non-Woven Carbon Nanofiber Mat Presence on Cure Kinetics of Epoxy Nanocomposites

Summary : An investigation was carried out into the cure kinetics of carbon nanofiber (CNF) mat-epoxy nanocomposites, composed of bisphenol-A based epoxy resin and diethylene triamine as a curing agent. It was observed that the rate of cure reaction for CNF mat-epoxy nanocomposites was higher than that for neat epoxy resin at low curing temperatures and the presence of the CNF mat produced the maximum influence at a certain curing temperature and time. At high curing temperature and long curing times, the effect of CNF mat on the cure rate was insignificant. The CNF mat-epoxy composite exhibited somewhat lower value of activation energy than that of the neat epoxy system at the beginning of the curing stage. The weight fraction of CNF mat also affected the cure reaction of epoxy nanocomposites at the same curing temperature. As the amount of CNF mat increased, the cure rate was higher at the same cure time. However, at high CNF mat loading, the cure reaction was retarded since the amount of epoxy and hardener decreased dramatically at high CNF contents together with the hindering effect of the CNF mat on the diffusion of epoxy resin and the curing agent, leading to lower crosslinking efficiency. Although the curing efficiency of epoxy nanocomposites dropped at high CNF mat content, the glass transition temperature (T_g) was still high due to the ultra-high strength of the CNF mat. The cure kinetics of CNF mat-epoxy nanocomposites was in good agreement with Kamal's model.     

Determination of glass transition temperature,thermal expansion and,shrinkage of epoxy resins

On the basis of measurements of linear thermal expansion of hardened epoxy resins the influence of some modifiers on the thermal expansion of epoxy resin Epidian-5 has been examined. The glass transition temperatures of examined samples were determined.The paper presents also results of the examinations of changes in thermal and cure shrinkage for epoxy resins that occur under the influence of such modifiers as plasticizers and fillers.Five different compositions were examined. A simple and fast measuring method was applied, in which sample elongations vs temperature were determined with a cathetometer. Specific volume changes of liquid resins with temperature were measured with a quartz dilatometer and a cathetometer.