The effect of kevlar fiber reinforcement on the curing,thermal, and dynamic‐mechanical properties of an epoxy/anhydride system

Curing, thermal, and dynamic‐mechanical relaxational behavior of an epoxy/‐anhydride resin and a Kevlar‐fiber/epoxy composite were compared. Reinforcement by Kevlar fibers had a catalytic effect on the curing reaction. Reinforced formulations produced higher extents of reaction than neat formulations at the same curing time. Curing kinetics was also studied by means of DSC heating scans. When the Kevlar content increased, the heat flow curves and the exothermic peak temperature shifted significantly to lower temperatures. The glass transition temperature of the matrix also decreased as the Kevlar content increased. Postcuring reduced the differences between the neat and reinforced formulations. Loss tangent and storage modulus versus frequency master curves were obtained from isothermal dynamic‐mechanical measurements. The effect of fiber addition on the main dynamic‐mechanical relaxation was analyzed with a simple mechanical model.     

Curing of unsaturated polyester resins with low exotherm peak

The curing behavior of an unsaturated polyester resin with low exotherm peak was studied by a standard procedure and by differential scanning calorimetry (DSC). A copper salt and α-methylstyrene were used as the polymerization retarders. The influence of the retarders on the exotherm peak temperature, gelation time, exothermic heat and the polymerization kinetics was investigated.     

Studies on the curing and thermal behaviour of DGEBA in the presence of bis(4‐carboxyphenyl) dimethyl silane

The curing behaviour of diglycidyl ether of bisphenol‐A (DGEBA) was investigated by differential scanning calorimetry using bis(4‐carboxyphenyl) dimethyl silane (CPA) as a crosslinking agent and imidazole as a catalyst. Two exotherms were observed in the absence of catalyst in the temperature range 166–328 °C. A significant decrease in the curing temperature was observed when 0.1% imidazole was used as catalyst. Further increase in the concentration of imidazole resulted in a decrease in the peak exotherm temperature. The effect of stoichiometry of functional groups on the curing behaviour of DGEBA was investigated by taking varying mole ratios of CPA, ranging from 1 to 2.5, keeping the concentration of imidazole as 0.1% w/w. The heat of polymerization (ΔH) was found to be maximum at a molar ratio of 1:1.75 (DGEBA:CPA). Mixtures of diaminodiphenyl sulfone (DDS and CPA or phthalic anhydride (PA) and CPA in ratios of 1:0, 0.25:0.75, 0.5:0.5, 0.75:0.25) were also used to investigate the curing behaviour of DGEBA. A significant decrease in curing temperature of DGEBA/DDS was observed on partially replacing DDS with CPA, whereas marginal change in the curing temperatures was observed on replacing phthalic anhydride with CPA. The thermal stability of epoxy resin, cured isothermally, was evaluated by recording thermogravimetry/dynamic thermogravimetry traces in nitrogen atmosphere. The percentage char yield was highest for the sample cured using 1.75 mole of CPA. Copyright © 2003 Society of Chemical Industry     

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.     

用红外光谱法研究环氧树脂基体的固化特性

用红外光谱法研究了芳纶抗弹复合材料中改性Ｆ－４６环氧树脂基体的固化特性,用环氧基团相对浓度的变化速率表征环氧树脂基体的固化反应速率。研究了环氧树脂基体的固化反应速率随固化剂含量、固化反应温度的变化规律;根据固化反应过程中环氧树脂基体的环氧基、酯基和醚基等各活性基团相对浓度的变化情况,探讨了环氧树脂基体的固化反应机理。     

The Role of Alumina Trihydrate Filler on semiflexible unsaturated polyester resin-4 and inhibition of double-base rocket propellants

The use of unsaturated polyesters for inhibition of double-base rocket propellants has become popular in recent years. A direct bonding inhibition system termed as semiflexible unsaturated polyester resin-4 has been recently developed and reported by us. It has been reported in literature that the use of some fillers such as antimony trioxide, titanium dioxide, lithophone, alumina trihydrate etc. impart better mechanical and heat resistance properties. The effect of 10% to 60% of alumina trihydrate (Al₂O₃ · 3 H₂O) on semiflexible unsaturated polyester resin-4 in respect of gel time, exotherm peak temperature, tensile strength, %-elongation, nitroglycerin absorption, water absorption, heat resistance and flame retardance has been studied and the result obtained have been discussed. It is observed that 30% of alumina trihydrate imparts desirable properties. The 108 mm and 148 mm-diameter propellant sustainers inhibited with resin-4 containing 30% alumina trihydrate and conditioned at ambient, sub-zero temperature (−40°C for 18 hr) and high temperature (+50°C for 18 hr) were statically evaluated. The pressure-time profiles at all temperatures have been found to be flat and neutral which infer that the inhibition system works satisfactorily.     

用DSC法研究环氧树脂/环氧封端酚酞聚芳醚腈的固化特性

利用差示扫描量热法研究了AG - 80环氧树脂和环氧封端酚酞聚芳醚腈 (简称E -PCE)共混物中固化剂含量对树脂基体固化反应温度、反应热的影响。此共混环氧树脂基体的最低固化反应温度为1 61 .3℃ ,固化反应表观活化能为 60 .66kJ/mol,固化反应级数为 0 .875。     

DSC法研究聚异氰酸酯／环氧树脂胶粘剂的固化反应动力学及固化工艺

采用差示扫描量热法(DSC)研究了聚异氰酸酯／环氧树脂的固化过程,研究了不同配比对固化反应的影晌,固化度与固化温度的关系,计算了固化反应表观活化能和反应级数,确定了聚异瓤酸酯／环氧树脂胶粘剂的固化工艺。结果表明:胶粘剂中固化剂的含量对环氧树脂的固化反应过程有显著的影响,随着聚异氰酸酯的增加,固化放热量增加。当聚异氰酸酯的含量达到1．2份时,固化反应放热量达到最大值;不同升温速率下,体系固化温度有很大差异,随着升温速率的提高,固化温度增加。通过动力学计算得到体系最佳固化温度为108℃,固化时间为6-8h,固化体系的活化能为43．31kJ／mol,反应级数为1．17。     

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.     

固化剂含量对玻纤增强酚醛复合材料性能的影响

通过动态力学分析、差示扫描量热分析和电性能测试,研究了固化剂六亚甲基四胺含量对玻纤增强酚醛复合材料性能的影响,并确定了固化工艺参数。结果表明:随着固化剂含量的增加,复合材料的储能模量提高,力学损耗峰变窄,峰值降低;与固化剂含量为6%时相比,当固化剂含量为10%时,复合材料的玻璃化温度提高了23℃,当固化剂含量为12%时,热变形温度提高了34℃;复合材料的冲击强度在固化剂含量为12%时达最大值,吸水率在固化剂含量为10%时达最小值;复合材料的电性能随着固化剂含量的增加而得到提高;固化剂含量10%时的复合材料的固化工艺为:凝胶温度145℃、固化温度156℃、后处理温度173℃。     

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     

螺环原碳酸酯/环氧树脂体系固化反应动力学

采用示差扫描量热法(DSC)对螺环原碳酸酯膨胀单体(SOC)/双酚A型环氧树脂(EP)体系的固化行为、放热峰进行了分析;并用Kissinger方程和Crane方程求得体系表观活化能、表观反应频率因子、反应级数等固化反应过程动力学参数,结果表明:螺环原碳酸酯膨胀单体的加入,体系的表观活化能和表观反应频率因子增加,反应级数保持不变,而反应速率急剧下降。此外,利用外延法对体系起始固化温度、恒温固化温度以及后处理温度进行初步探讨,为固化工艺的确定提供了依据。     

含亚甲基链段柔性固化剂的制备与性能研究

以双官能度EP(环氧树脂)对脂肪族二胺进行改性,制备了含多段长亚甲基链段的柔性固化剂。采用FT-IR(红外光谱)法、TGA(热失重分析)法、非等温DSC(差示扫描量热)法和β-T(升温速率-温度)外推法等对改性固化剂的结构、改性固化剂/EP胶粘剂的性能(包括热稳定性、动态力学参数和最佳固化温度等)进行了分析和验证。结果表明:改性固化剂/EP胶粘剂固化体系的表观活化能为86.73 kJ/mol、反应级数为1.24和最佳固化温度为66℃;当n(EP):n(改性固化剂)=1:0.50时,相应胶接件的-196℃、室温、60℃剪切强度分别为16.84、14.73、13.52 MPa,说明其强度和韧性俱佳,并且完全满足实际使用要求。     

紫外光固化环氧豆油丙烯酸酯的制备与表征

将环氧大豆油与丙烯酸反应制备出环氧豆油丙烯酸酯预聚物,讨论了反应温度、反应时间、催化剂、阻聚剂的种类与用量对合成反应的影响,并用红外光谱对产物的结构进行了表征。研究结果表明其最佳反应条件是:催化剂三苯基膦,反应温度110℃,反应时间8h。该预聚树脂可用紫外光固化,其固化膜硬度达3H,且具有较好的柔韧性和附着力。     

Effect of oxirane groups on curing behavior and thermal stability of vinyl ester resins

The effects of oxirane groups in vinyl ester (VE) resin and reactive diluent on curing characteristics and thermal behavior of cured resins are described. Stoichiometric (0.5:1, sample A) as well as nonstoichiometric (0.5:0.85, sample B) ratios of the diglycidyl ether of bisphenol-A (DGEBA) and methacrylic acid (MA) were used for the synthesis of VE resins. Resin sample B had more residual epoxy groups because of the stoichiometric imbalance of the reactants. VE resins thus obtained were diluted with methyl methacrylate (MMA; 1:1, w/w), and controlled quantities of epoxy groups were introduced by partial replacement of MMA with glycidyl methacrylate (GMA), keeping the overall ratio of resin and reactive diluent constant. Increase of GMA content in resin A or B resulted in a decrease in gel time, indicating that the curing reaction is facilitated by the presence of epoxy groups. An increase in initiator content also reduced the gel time. In the differential scanning calorimetry (DSC) scans, a sharp curing exotherm was observed in the temperature range 107 ± 3–150 ± 1 °C. The onset temperature (T_onset) and peak exotherm temperature (T_exo) decreased with increase in GMA content. Heat of curing (ΔH) also increased with increase in GMA content. A broad exotherm was observed after the initial sharp exotherm that was attributed to the etherification reaction. Cured VE resins were stable up to 250–260 °C, and started losing weight above this temperature. Rapid decomposition was observed in the temperature range 400–500 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 416–423, 2001     

改性2-甲基咪唑微胶囊促进剂的研究

以改性2-甲基咪唑为芯材,聚醚酰亚胺为壳材,采用喷雾干燥法制备了一种微胶囊型中温固化促进剂,并对其结构、粒径分布、表面形貌、固化活性及贮存稳定性进行了表征。壳芯质量比为1∶2时制得的微胶囊表面光滑,粒径分布较窄,平均粒径为306.1nm。经DSC测试,由双酚A型环氧树脂、双氰胺、微胶囊组成的固化体系的放热峰温度为148.6℃。贮存稳定性试验表明固化体系的贮存稳定性良好,25±3℃下贮存期超过32d。计算得到固化体系表观活化能为86.89kJ/mol。     

Curing and Morphology of BPA Epoxy Resin/LC Epoxy Resin PEPEB Composites

Liquid crystalline epoxy resin (LC epoxy resin) – p-phenylene di{4-[2-(2,3-epoxypropyl)ethoxy]benzoate} (PEPEB) was synthesized. The mixture of PEPEB with bisphenol-A epoxy resin (BPAER) was cured with a curing agent 4,4-diamino-diphenylmethane (DDM). The curing process and thermal behavior of this system were investigated by differential scanning calorimeter (DSC) and torsional braid analysis (TBA). The morphological structure was measured by polarizing optical microscope (POM) and scanning electron microscope (SEM). The results show that the initial curing temperature Ticu (gel point) of this system is 68.1°C, curing peak temperature T _pcu is 102.5°C, and the disposal temperature T _fcu is 177.6°C. LC structure was fixed in the cured epoxy resin system. The curing kinetics was investigated by dynamic DSC. Results showed that the curing reaction activation energy of BEPEB/BPAER/DDM system is 22.413 kJ/mol. The impact strength is increased 2.3 times, and temperature of mechanical loss peak is increased to 23°C than the common bisphenol-A epoxy resin, when the weight ratio of BEPEB with BPAER is 6 100.     

液化竹基酚醛树脂/竹粉复合体系固化动力学研究

采用非等温差热分析(DTA)研究了竹粉(PB)对液化竹基酚醛树脂(PBF)固化行为及固化动力学的影响,求出固化反应的表观活化能、反应级数及频率因子等参数,进而建立了复合体系的固化反应动力学模型。实验结果表明:加入竹粉后,体系的固化峰顶温度、表观活化能、反应级数和频率因子分别降低至110.5℃、57.27kJ.mol-1、1.0079、1.99×105 s-1(纯PBF树脂的上述指标分别为122.5℃、63.46 kJ.mol-1,1.0173和8.04×105 s-1),竹粉的加入加速了PBF的固化反应过程。     

Cure and properties of unfoamed polyurethanes based on uretonimine modified methylene–diphenyl diisocyanate

The curing behaviour of a series of polyurethanes based on modified methylene–diphenyl diisocyanate (MDI) and poly(propylene oxide) polyols was studied using isothermal Fourier‐transform infrared spectroscopy (FTIR), temperature‐ramped differential scanning calorimetry (DSC) and adiabatic exotherm experiments. The effects of catalyst type and content, and of polyol molecular weight and functionality on the curing behaviour of the material were investigated. Increasing catalyst concentration or decreasing the polyol molecular weight raised the rate of reaction and shifted the DSC peak exotherm temperature to lower temperatures, but the heat of reaction was effectively constant. A marked increase in reaction rate was observed when a 1 °‐alcohol‐based polyol (from ethylene oxide end‐capping) was used in place of the standard poly(propylene oxide) end‐capped 2 °‐polyols. FTIR isocyanate conversion during polyurethane formation for a range of dibutyltin dilaurate (DBTDL) concentrations was satisfactorily fitted to second‐order kinetics. An approximately linear relationship between DBTDL catalyst concentration and reaction rate constant was found, but increasing the concentration of DBTDL was found to have no significant effect on the magnitude of the activation energy. The activation energy for polymerization was found to be independent of the molecular weight of the diol or triol systems. Dynamic mechanical thermal analysis revealed a linear increase of the glass transition temperature with decreasing triol weight fraction, and was in good agreement with a theoretical model based on copolymer and crosslinking effects. © 2000 Society of Chemical Industry