曼尼希碱环氧树脂固化剂的研究进展

阐述了曼尼希碱型环氧树脂固化剂的合成原理、合成方法和发展历史与发展趋势,并就增加固化剂韧性、耐热性、降低固化剂黏度和开发水下固化剂以及改进固化剂生产工艺等方面进行了探讨。     

Synthesis and reactivity of Mannich-derived polyoxyethylene amines as epoxy curing agents

The facile Mannich reaction of phenol, formaldehyde, and polyoxyalkylene polyamines at various molar ratios afforded a family of polyetheramines containing functionalities of phenol, primary amines, secondary amines, and polyoxyethylene or polyoxypropylene block copolymers in the same molecule. The synthesis can be generalized by using various polyoxyethylene or polyoxypropylene diamines (and triamines) of molecular weights ranging from 104 to 430 to prepare a family of Mannich amines, with exception of certain gel products such as phenol/formaldehyde/bis(aminoethyl)ether adduct at 1 : 3 : 3 molar ratio. The series of Mannich amines were evaluated for their epoxy curing reactivities by comparing their gel time and drying time. The Mannich amines prepared from polyoxyethylene amines exhibited higher reactivities than those of polyoxypropylene amine derivatives. The trend of their relative reactivities is explained by the molecular size, the multiplicity of amines in the molecule, and the steric hindrance of amine structure. The physical properties of cured epoxy materials, such as impact, tensile, flexural strength, and hardness properties were also measured and correlated with the amine molecular weight, crosslinking density, and the presence of phenol group. The structure–property relationship is discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2339–2346, 1997     

Studies on curing kinetics and thermal behavior of phosphorylated epoxy resin in the presence of aromatic amide‐amines

This article describes the synthesis of some novel aromatic amide‐amine curing agents by reacting 1 mole of p‐amino benzoic acid with 1 mole of each of 1,4‐phenylene diamine (P), 1,5‐diamino naphthalene (N), 4,4′‐(9‐fluorenyllidene)‐dianiline (F), 3,4′‐oxydianiline (O), and 4,4′‐diaminodiphenyl sulphide (DS) and were designated as PA, NA, FA, OA, and SA, respectively. The aromatic amide‐amines so synthesized were characterized with the help of spectroscopic techniques, viz., Fourier Transform Infrared, proton nuclear magnetic resonance, and carbon nuclear magnetic resonance. The curing kinetics of the epoxy resins obtained by reacting amines with diglycidyl ether of bisphenol‐A blended with tris(glycidyloxy)phosphine oxide in a ratio of 3 : 2, respectively, were investigated by DSC technique using multiple heating rate method (5, 10, 15, 20°C/min). Activation energies were determined by fitting the experimental data into Kissinger and Flynn‐Wall‐Ozawa Kinetic models. The activation energies obtained through Flynn‐Wall‐Ozawa method were slightly higher than Kissinger method but were comparable. However, both the energies were found to be dependent on the structure of amines. The thermal stability and weight loss behavior of isothermally cured thermosets were also investigated using thermogravimetric analysis in nitrogen atmosphere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

阻燃型胺类环氧树脂固化剂的研究进展

介绍了近年来胺类环氧树脂固化剂改性的一个重要方面——阻燃型胺类环氧树脂固化剂,及其阻燃性、耐热性的研究进展。阻燃型胺类环氧树脂固化剂主要包括含磷、含氮杂环、含硅胺类固化剂,以及含氮磷杂环和含硅-磷胺类固化剂。     

Preparation and epoxy curing of p‐nonylphenol/dicyclopentadiene adducts

Phenol/dicyclopentadiene adducts were prepared from the BF₃‐catalyzed reaction of p‐nonylphenol and dicyclopentadiene at molar ratios of 2 : 1 and 3 : 2. These dicyclopentadiene‐derived novolac products contain tricyclodecane and multiple phenol functionalities. In curing with diglycidyl ether of bisphenol A, the polymer properties were compared with those cured with formaldehyde novolac or Jeffamine D‐400 amine. When p‐nonylphenol/dicyclopentadiene adducts were mixed with other commercially available curing agents such as Jeffamine D‐400 amine, the tricyclodecane functionality was introduced into the resulting epoxy network. The flexibility of the cured resin was improved due to the presence of the tricyclodecane moiety in the polymer structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2196–2206, 1999     

Synthesis and epoxy curing of Mannich bases derived from bisphenol A and poly(oxyalkylene)diamine

A family of Mannich bases were prepared from the reaction of 2,2‐bis‐(4‐hydroxyphenyl)propane (bisphenol A or BPA), formaldehyde, and poly(oxyalkylene)diamines at 1 : 1 : 1 or 1 : 2 : 2 molar ratio. By varying the molar ratio of bisphenol A to amine and the chemical structures of poly(oxyalkylene)diamines, a series of products with multiple functionalities of primary/secondary amines, phenols, and poly(oxyalkylene) were prepared. The curing profiles of these products toward the diglycidyl ether of bisphenol A (DGEBA) were examined by a differential scanning calorimeter (DSC). The physical properties of these cured materials were correlated with the chemical structures of the Mannich bases. Compared with the poly(oxyalkylene)diamines, the built‐in phenol moiety in Mannich bases accelerated the curing rate. Both amine and phenol functionalities could be reactive sites toward diglycidyl ethers in a step‐wise fashion under catalytic (triphenylphosphine) and different temperature conditions. Furthermore, the cured polymers demonstrated improved properties including tensile and flexural strength in comparison with those cured by the corresponding poly(oxyalkylene)diamines. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 615–623, 2000     

曼尼希改性二乙烯三胺环氧建筑胶固化剂的制备

选用苯酚（P）、甲醛（F）对二乙烯三胺（DETA）进行曼尼希反应改性,研究了产物黏度、胺值与原料配比的关系。将改性的固化剂与环氧树脂E51进行配胶浇注,研究了胶体的力学性能与潮湿环境下的粘接性能。结果表明,P、DETA与F物质的量比[n（P）：n（DETA）：n（F）]=1．5：1．5：1．5的产物综合性能最佳。该固化剂黏度适宜（6542mPa·s）,与E51配胶浇注后,拉伸强度为40MPa,压缩强度达80MPa,潮湿环境下的钢一钢剪切强度为9．2MPa,与混凝土的粘接拉伸强度达47MPa,为混凝土内聚破坏。     

环氧建筑结构胶固化速度的调整

在建筑结构加固领域用环氧树脂中,选一种高活性酚醛胺固化剂HD—SG和一种低活性改性芳香胺固化剂HD—MG,通过调整HD-SG／HD—MG的质量比,可以得到不同活性的环氧树脂固化剂,并对固化物力学性能进行研究。     

Ultraviolet‐curing behavior of an epoxy acrylate resin system

Ultraviolet (UV)‐curing behavior of an epoxy acrylate resin system comprising an epoxy acrylate oligomer, a reactive diluent, and a photoinitiator was investigated by Fourier transform infrared (FTIR) spectroscopy. The conversion changes of the resin system containing 20 phr of 1,6‐hexanediol diacrylate as a reactive diluent and 2‐hydroxy‐2‐methyl‐1‐phenyl‐propan‐1‐one as a photoinitiator were measured under different UV‐curing conditions. The fractional conversion was calculated from the area of the absorption peak for the vinyl group vibration occurring at 810 cm^?1. The effects of photoinitiator concentration, total UV dosage, one‐step or stepwise UV irradiation, UV intensity, atmosphere, and temperature on the curing behavior of the resin system were investigated. The conversion of the resin system increased rapidly at the initial stage of the UV‐curing process but increased very slowly after that. The final conversion of the resin system was mainly affected by total UV dosage. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1180–1185, 2005     

新型环氧固化剂的合成及固化动力学研究

介绍了2步法合成1,4-双(2,4-二氨基苯氧基)苯(14BDAPOB)的方法,并将其用作环氧树脂固化剂。采用非等温差示扫描量热法(DSC)对酚醛环氧树脂/14BDAPOB的固化过程进行了研究,并利用Kissinger、Crane和Arrhenius方程对该固化反应进行了动力学分析,求得了体系的固化动力学参数;测定了体系的拉伸剪切强度。结果表明,体系的活化能为66.97 kJ/mol,反应级数为0.90;经14BDAPOB固化后的酚醛环氧体系拉伸剪切强度可达21.3 MPa。     

Polymeric reagents: Part 1. Synthesis of polymer-anchored amines useful for curing epoxy resins

A range of polymers carrying amino-functions [NHEt, NHBuⁿ, NEt₂, NPr, N(CH₂CH₂CH₂NH₂)₂, NMeCH₂CH₂CH₂NH₂ or NEtCH₂CH₂CH₂ NH₂] has been synthesised via amination of styrene-vinylbenzyl chloride copolymers, poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether), and via homopolymerisation and copolymerisation (with styrene) of (n-butyl)(vinylbenzyl)-ammonium chloride. Some of the polymers showed promise as curing agents for epoxy resins.     

水性环氧固化剂分散体的制备及改性

采用不同分子量的聚乙二醇与液体环氧树脂EPON828合成反应型乳化剂,然后将反应型乳化剂链段引入到以液体环氧树脂EPON828与间苯二甲胺为原料合成的端胺基中间体的分子结构中,再用活性稀释剂进行封端,最后加水分散,制得水性环氧固化剂分散体。采用了γ-氨丙基三乙氧基硅烷(即硅烷偶联剂KH-550)对其进行改性。确定了间苯二甲胺与环氧树脂EPON828的摩尔比为2.2∶1,聚乙二醇6000与环氧树脂EPON828(摩尔比为1∶1)制备的反应型乳化剂用量为9%,硅烷偶联剂KH-550的用量为固化剂分散体的质量的2%时,所制备的水性环氧固化剂分散体稳定性最佳,其粒径为750.8nm,固含量约60%,胺值为118mgKOH/g,黏度为4500mPa·s。室温固化后,涂膜硬度为3H,光泽度(60°)为108%,冲击强度50kg·cm,柔韧性1mm,附着力1级,耐酸碱腐蚀性能好。通过傅立叶变换红外光谱表征了反应产物。     

Synthesis of rosin‐based imidoamine‐type curing agents and curing behavior with epoxy resin

Rosin is an abundantly available natural product. The characteristic fused ring structure of rosin acids is analogous to that of some aromatic compounds in rigidity, and makes rosin and its derivatives potential substitutes for those aromatic compounds. In the study reported, the synthesis of biobased curing agents containing imide structure using rosin and the cure reaction were investigated. Rosin‐based imidoamine‐type curing agents were synthesized, and the chemical structure was confirmed using ¹H NMR, Fourier transform infrared and electrospray ionization spectroscopy. The curing behavior with diglycidyl ether of bisphenol A epoxy was studied using differential scanning calorimetry. The thermal mechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetry, respectively. The results indicate that the curing behavior of the rosin‐based curing agents is similar to that of curing agents with analogous structures. Cured products have good thermal stability due to the presence of the imide group and the bulky hydrogenated phenanthrene ring structure. Rosin acids have a great potential in the synthesis of epoxy curing agents as replacements for some of the current commercial aromatic or cycloaliphatic analogues. Copyright © 2010 Society of Chemical Industry     

新型环氧树脂胶粘剂的固化动力学研究

在不同升温速率下采用非等温差示扫描量热（DSC）技术对一种新型改性环氧树脂胶粘剂的固化反应过程进行了跟踪,并利用Kissinger、crane方程以及Arrhenius方程对该固化反应进行了动力学分析。结果表明,该固化反应的活化能为59.18kJ／mol,反应级数为0．89;结合Dsc谱图确定其固化工艺为130℃／1h＋150℃／2h＋175℃／3h。     

新型潮湿表面用固化剂的合成

以间苯二甲胺(MXDA)和环氧氯丙烷(ECH)为原料,在物料物质的量比(MXDA/ECH)为2.1/1,反应温度为60℃,反应时间为2.5 h的工艺条件下合成环氧-胺加成物。然后与N,N-二甲基甲酰胺(DMF)反应,端胺基-多胺加成物与DMF的物质的量的比为1∶2.4,温度为110℃;最后用单环氧化合物封掉多余仲胺生成了一种新型可潮湿固化的固化剂(H-APMD)。对合成条件进行了优化。采用红外光谱法确定了分子结构。采用热重分析研究了涂膜的性能。结果表明,该固化剂是一种优良的潮湿固化固化剂。     

Preparation and analysis of a flexible curing agent for epoxy resin

A kind of novel aromatic amine bis(4‐nonyl‐2,5‐diamine‐penoxyl)alkylate (RA_n) as curing agents for epoxy resins were prepared through three steps of reactions using nonyl phenol and dibromoalkylate as materials. Dynamic mechanical analysis (DMA) indicated that the secondary relaxation for the resins cured by RA_n were generated by the nonyls in RA_n molecules when temperature was below ?50°C. Comparing with other reference resins, the enhancement for toughness of RA_n cured‐resins were at least 15%, which were contributed by such secondary relaxation. Furthermore, stiffness of the networks and thermal properties of the resins were not influent by the flexible groups (nonyl) in RA_n after curing, since the groups were located only in the branched chains of the networks. The mechanical and thermal properties of the new material have been significantly enhanced. The relevant method and procedure developed through this research have been granted Chinese patent recently (Yang and Gong, Chin. Pat. CN1978483A, 2007). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

环氧片状模塑料用微胶囊固化剂的制备

以2-乙基-4-甲基咪唑(2E4MI)为芯材、聚乙二醇(PEG-6000)为壁材,采用熔融喷雾法制备了一种环氧片状模塑料用微胶囊固化剂。对微胶囊进行了表征,对环氧树脂的固化行为进行了研究。研究表明,该胶囊固化剂中囊芯材料2E4MI的质量分数约为l3.7%。ESMC的最佳固化工艺确定为:101℃/10min+111℃/10min+150℃/10min+180℃/10min。微胶囊化固化剂中的PEG-6000壁膜在常温下可以阻止环氧树脂的固化,使ESMC树脂糊体系具有更好的室温贮存稳定性。固化剂的微胶囊化不会引起固化机理的变化。环氧树脂的固化度α可达0.93。     

Curing and post‐curing luminescence in an epoxy resin

A spontaneous luminescence is reported when epoxy resin samples are heated in air. This phenomenon is very sensitive to the nature of the atmosphere. The same treatment in nitrogen leads to an extinction of the luminescence. The emission process is restored when samples are kept for a sufficient time in air. To better understand this phenomenon, we have investigated the luminescence of the elementary constituents of the epoxy (resin and hardener), when heated in air and nitrogen, as well as during resin‐curing in the same atmospheres. It appears that the emission process is linked with the presence of oxygen. Although the kinetics of the luminescence can differ, depending on the nature of the sample (cured resin, resin during curing, liquid components), the emission spectra are the same during resin‐curing and upon heating of the cured resin and hardener. The emission spectrum of the base resin is different. It is concluded that the light results from a chemiluminescence process during oxidation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1899–1904, 2006     

新型环氧树脂固化剂的合成及其环氧胶粘剂

以4,4’-二氨基二苯甲烷为原料,经乙酰化、硝化、酸解、还原、中和5步反应合成得到了一种新型环氧树脂固化剂,即3,3’,4,4’-四氨基二苯甲烷,并通过FT—IR分析及熔点测定对其进行了表征。此外,对改性环氧树脂／3,3’,4,4’-四氨基二苯甲烷体系也作了性能研究。