环氧树脂和环氧/环硫树脂与胺的固化反应动力学

采用非等温DSC法对低黏度体系CY184/IPDA环氧树脂体系及对CY184/ES184/IPDA环氧/环硫树脂体系的固化反应动力学进行了研究。用高级等转化率Vyazovkin积分法求取活化能E_a,通过Málek法确定了固化反应机理函数和动力学参数,得到固化反应动力学方程。结果表明:CY184/IPDA环氧树脂体系的平均活化能为47.04 kJ·mol^-1;CY184/ES184/IPDA环氧/环硫树脂体系的活化能为48.97 kJ·mol^-1。两种体系的模型拟合曲线与实验得到的DSC曲线吻合得较好,均符合esták-Berggren(m,n)模型。     

Dielectric analysis of the cure of thermosetting epoxy/amine systems

A low molecular weight epoxy resin is cured isothermally with an aromatic amine hardener, and the dielectric properties are measured as a function of the frequency, reaction time, and cure temperature. At specific stages in the cure, small samples from the reacting mixture are quenched and subsequently analyzed for the glass transition temperature and epoxy group conversion by differential scanning calorimetry. In this manner, the change In dielectric properties can be directly correlated with the network structure. The ionic conductivity is modeled as a function of the cure temperature and the cure-dependent glass transition temperature using a Williams-Landel-Ferry (WLF) relation. Combining this WLF relation with the DiBenedetto equation, a comprehensive model relating conductivity with the extent of reaction and cure temperature has been developed.     

Torsional braid analysis of the aromatic amine cure of epoxy resins

The cure behavior of diglycidyl ether of bisphenol A (DGEBA) type of epoxy resins with three aromatic diamines, 4,4′-diaminodiphenyl methane (DDM), 4,4′-diaminodiphenyl sulfone (44DDS), and 3,3′-diaminodiphenyl sulfone (33DDS) was studied by torsional braid analysis. For each curing agent the stoichiometry of the resin mixtures was varied from a two to one excess of amino hydrogens per epoxy group to a two to one excess of epoxy groups per amino hydrogen. Isothermal cures of the resin mixtures were carried out from 70 to 210°C (range depending on epoxy—amine mixture), followed by a temperature scan to determine the glass transition temperature (T_g). The times to the isothermal liquid-to-rubber transition were shortest for the DDM mixtures and longest for the 44DDS mixtures. The liquid-to-rubber transition times were also shortest for the amine excess mixtures when stoichiometry was varied. A relatively rapid reaction to the liquid-to-rubber transition was observed for the epoxy excess mixtures, followed by an exceedingly slow reaction process at cure temperatures well above the T_g. This slow process was only observed for epoxy excess mixtures and eventually led to significant increases in T_g. Using time—temperature shifts of the glass transition temperature vs. logarithm of time, activation energies approximately 50% higher were derived for this process compared to those derived from the liquid-to-rubber transition. The rate of this reaction was virtually independent of curing agent and was attributed to etherification taking place in the epoxy excess mixtures. © 1994 John Wiley & Sons, Inc.     

Dielectric studies of water in epoxy resins

Dielectric measurements are reported on amine-cured epoxy resin samples over a frequency range from 200 Hz to 200 kHz and a temperature range from ?60°C to 70°C as a function of molecular weight of the diglycidyl ether and water content. The effects of change of the molecular weight of the diglycidyl ether on the dielectric relaxation are small in comparison with the changes observed on the introduction of water into the matrix. Analysis of the data indicates the presence of cluster—free and bound—molecularly dispersed water. The former are presumed to be found in voids and cavities which arise in curing powder samples. The conductivity of the water-doped samples reflects the mobility of the water and is compared with the predictions of theories for amorphous materials.     

Comparison of microwave and thermal cure of an epoxy/amine matrix

An investigation was carried out into the effect ofa microwave cure on an epoxy prepolymer with a cycloaliphatic diamine mixture, as compared to a standard thermal cure. The microwave waveguide and process (propagation mode TE₀₁) were adjusted to obtain large homogeneous samples. The extent of reaction, x, was measured during the microwave processing by size exclusion chromatography and differential scanning calorimetry. A good estimate of x was found using a modified DiBenedetto equation correlating x and the glass transition temperature T_g. The homogeneity of the samples was checked during the last steps of cure, showing the efficiency of the microwave processing and waveguide. The influence of the nature of the mold (metallic or dielectric) on the reaction kinetic was also investigated. Samples cured by both thermal and microwave processing were characterized by dynamic and static mechanical properties and then compared with those of fully crosslinked networks, i.e., postcured at a high temperature.     

The boron trifluoride monoethyl amine complex cured epoxy resins

The curing exotherm pattern is affected by the equivalent ratio of curing agent, boron trifluoride monoethylamine complex (BF₃ · MEA), to epoxy resin. The diglycidyl ether of 9,9-bis(4-hydroxyphenyl) fluorene (DGEBF) cures more slowly than the diglycidyl ether of bisphenol A (Epon 828). The glass transition temperatures (T_g's) of BF₃ · MEA cured Epon 828 are increased with inceasing concentration of curing agent (0.0450–0.1350 eq.) cured DGEBF. The activation energies for the thermal decomposition for BF₃ · MEA (0.0450–0.1350 eq.) cured DGEBF. The activation energies for the thermal decomposition for BF₃ · MEA (0.0450 eq./epoxy eq.) cured Epon 828 and DGEBF are almost equivalent 43 and 44 kcal/mol, respectively. DGEBF when added to DGEBA improves the T_g and char yield with the BF₃ · MEA curing system. The T_g of both resin systems can be increased by longer post cure, whereas the char yield does not appear to change significantly. No ester group formation is found for the BF₃ · MEA-cured DGEBF, although this has been previously reported for the DGEBA system. The BF₃ · MEA cure at 120°C is better than at 140°C because of vaporization and degradation of the curing agent at the higher temperature. The rapid gelation of the epoxy resin may be another reason for the lower degree of cure at high temperature.     

Model compound studies on the amine cure of epoxy resins

Monoepoxy phenyl glycidyl ether, curing agent p-chloroaniline, and the substituted urea type accelerator Monuron were used as a model system for studying the amine cure of epoxies. Reactions were carried out at 120°C with amine to epoxy equivalent rations of 0.25 and 1.0 Reaction mixtures were analyzed primarily by reverse phase high performance liquid chromatography. Three types of reactions occur; simple amine addition to epoxy, homopolymerization of epoxy, and epoxy polymerization involving the addition products. In the absence of accelerator the reaction involved simple addition. With the accelerator, there was competition between addition and polymerization, the balance depending on the amine to epoxy equivalent ratio. Both addition and polymerization were important for a ratio of 1, but polymerization far outweighed addition for a ratio of 0.25.     

Comparison of microwave and thermal cure of epoxy resins

Stoichiometric mixtures of DGEBA (diglycidyl ether of bisphenol A)/DDS (diaminodiphenyl sulfone) and DGEBA/mPDA (meta phenylene diamine) have been isothermally cured by electromagnetic radiation and conventional heating using thin film sample configurations. Fourier transform infrared spectroscopy (FTIR) was used to measure the extent of cure. Thermal mechanical analysis (TMA) was used to determine the glass transition temperatures directly from the cured thin film samples. Well-defined glass transitions were observed in the TMA thermograph for both thermal and microwave cured samples. Significant increases in the reaction rates have been observed in the microwave cured DGEBA/DDS samples. Only slight increases in the reaction rates have been observed in the microwave cured DGEBA/mPDA samples. Higher glass transition temperatures were obtained in microwave cured samples compared to those of thermally cured ones after gelation. The magnitude of increases of glass transition temperature is much larger for the DGEBA/DDS system than DGEBA/mPDA system. The microwave radiation effect was much more significant in DGEBA/DDS system than in DGEBA/mPDA system. DiBenedetto's model was used to fit the experimental T_g data of both thermal and microwave cured epoxy resins.     

有机胺类固化环氧树脂热变形温度的实验研究

研究了脂肪族胺类固化环氧树脂热变形温度(HDT)。利用正交试验研究了固化工艺、固化剂、填料及环氧树脂4种因素对HDT的影响。结果表明,固化工艺是影响HDT的最显著因素,80℃固化3 h后HDT较常温7 d固化可提高约40℃,且平均挠度变化率最小。本文研究了在高温固化工艺下,不同结构固化剂对无填料体系胶粘剂HDT的影响。结果表明,在不同的固化工艺下,使用不同结构脂肪胺类固化剂的HDT不同,过分提高固化温度反而会降低固化体系的耐热性能。     

Chemiluminescence from amine cured epoxy resins modified with halogenated phenylglycidyl ethers

Chemiluminescence from thermooxidized epoxide alone and that modified with phenyl glycidyl ethers has been investigated in isothermal and nonisothermal regime. Isothermal curves are characterized by a monotonous fall of chemiluminescence intensity from some initial value to very low levels of light emission. Nonisothermal curves show a maximum intensity at temperatures above 473 K. The luminescence intensity is influenced by both T_g and thermal stability of epoxide. The higher T_g or higher thermal stability brings about the higher intensity of light emission and vice versa. © 1994 John Wiley & Sons, Inc.     

Thermal modification of amine cured epoxy resins - thermal and mechanical studies

Mechanical test data are reported on lap joints and tensile test specimens which have been subjected to a defined post cure cycle. The mechanical properties exhibited an apparently systematic variation with temperature. Inspection of the resins indicated that chemical modification does not appear to occur to a significant extent below 433K. The change in the strength of the joints tensile test samples are discussed in terms of the relative importance of physical and chemical changes on the mechanical properties. It is evident that in the presence of oxygen considerable chemical modification can occur and this is observed both in terms of a change in colour of the resin and the appearance of voids.     

Dielectric studies of three epoxy resin systems during microwave cure

Dielectric properties of three curing epoxy resin systems at an industrial microwave frequency, 2.45 GHz, were measured over a temperature range lower than the cure temperature. Extent of cure, which is determined by DSC, is used to describe the progress of the polymerization. It has been found that, normally, the real and the imaginary part of the complex dielectric constant increased with temperature and decreased during microwave cure. The changes of the dielectric properties during the reaction are related to the decreasing number of the dipolar groups in the reactants and the increasing viscosity. The Davidson-Cole model can be used to describe the experimental data. The Zong model is applicable to polymeric materials at high microwave frequencies and can be used to calculate the parameters of the Davidson-Cole model. The epoxy resins exhibit one γ relaxation, which can be described by the Arrhenius rate law. The evolutions of the parameters in the models are discussed.     

Rubber-modified epoxy resins: 2. Dielectric and ultrasonic relaxation studies

Dielectric and ultrasonic relaxation measurements are reported on a series of rubber-modified epoxy resins over a temperature range from 190 to 423K. The resins were prepared by the reaction of the diglycidyl ether of bisphenol A with a chain-extender formed from carboxyl-terminated acrylonitrile-butadiene copolymer and cured with either triethylene tetramine or diethylene glycol bis-propyl amine. At low temperature, a dielectric relaxation was detected which was also active ultrasonically and can be associated with molecular motion of the acrylonitrile-butadiene chain extender. Changes in the concentration of the rubbery phase and type of curing agent used have marked effects on both the activation energy for molecular relaxation and in the breadth of the relaxation curves. Extensive studies of the dielectric properties at higher temperatures failed to reveal a resolvable relaxation associated with either of the higher temperature transitions observed using equilibrium measurements. Electrical conductivity, permittivity and acoustic velocity measurements performed as a function of temperature, however, indicate the existence of a change in slope at approximately the value of the glass transition of the epoxy phase. A further change in slope at approximately the temperature of the highest temperature transition was detected. The observed relaxation properties are compatible with the resins being phase-separated at low rubber concentrations and changing to a semicontinuous interpenetrating network structure at higher rubber concentrations.     

Dielectric relaxation during isothermal curing of epoxy resin with an aromatic amine

The isothermal curing behavior of an epoxy resin system has been monitored by a dielectric measurement whose sensor consisted of a vertical parallel-plate cell based on a three-terminal method. The materials used in the isothermal cure were the diglycidyl ether of bisphenol-A (DGEBA), which was purified from Epon 825 by recrystallization, and 4,4′-diamino diphenyl methane (DDM). A dielectric relaxation was observed during each isothermal cure at temperatures of 70,80,90, and 100°C, which were below the glass transition temperature (T_g) of the reactive DGEBA–DDM system at the gel point. The relaxation is considered to be caused by the transformation from a liquid state to an ungelled glassy state as a result of an increase in molecular weight because gelation followed by a rubbery state did not exist in the temperature range studied. The dielectric relaxation for the DGEBA–DDM system fits the empirical model of the Havriliak–Negami equation. The T_g of the DGEBA–DDM system, which was estimated from the dielectric relaxation time, agreed with the one experimentally determined by differential scanning calorimetry (DSC).     

脂环族环氧树脂／双酚A环氧树脂共混改性研究

采用脂环族环氧树脂（EPL-4221）与双酚A型环氧树脂E-51共混,用酸酐固化剂和促进剂使其固化,研究脂环族环氧树脂的用量对共混树脂性能的影响及其规律性,包括冲击强度、弯曲强度、拉伸强度、维卡软化点温度、漆膜的粘附力、铅笔硬度、耐磨性以及拉伸剪切强度。结果表明,随脂环族环氧树脂用量的增加,共混树脂的综合性能先增加后降低,脂环族环氧树脂的质量分数为15％-20％时,具有最大值。     

Investigation of influence factors in electron beam curing of epoxy resins using a calorimetry technique

Because of the complexity of the electron beam (EB) curing process, current understanding of EB curing of polymer resins and composites is limited. This article describes an investigation of different factors affecting EB curing of epoxy resin such as dose rate, time interval between irradiation doses, moisture, and photoinitiator concentration using a calorimetry technique. Results show that higher dose rate resulted in a higher and faster temperature increment in the uncured resin samples, and thus a higher degree of cure. In the multiple‐step EB irradiation, a shorter time interval between irradiation doses resulted in higher temperature in the resin samples and therefore higher degree of cure. Results indicate that moisture could delay crosslinking reaction in the early stages of the cure reaction, but accelerates it later in the curing process. Given a reasonable percentage of photoinitiator, experiments confirmed that samples with higher photoinitiator concentration reach higher degree of cure under same EB irradiation conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Use of inverse gas chromatography to quantify interactions in amine cured epoxy resins

Flory–Huggins interaction parameters, λ, were determined for a series of probes in an amine cured epoxy resin matrix (433–493 K) and its precursors (324–363 K) by inverse gas chromatography (IGC). Hildebrand–Scatchard theory was combined with Flory–Huggins theory in order to estimate infinte dilution solubility parameters (δ₂) for the matrix and its precursors at 298 K. It was shown that the value of the solubility parameter for the cured resin matrix lies between those of its precursors. Compared to the majority of published work, an unusual aspect of this application of IGC is that solubility parameters have been determined when the stationery phases are (i) small molecules and (ii) a highly crosslinked polymer. Moreover, all possible attempts have been made to ensure equilibrium conditions between probe and stationary phase, and compensation for asymmetry of peak profile has been applied in determining δ₂. The solubility parameters estimated by IGC are in good agreement with those calculated by other methods.