Liquid-rubber-modified epoxy adhesives cured with dicyandiamide. I. Preparation and characterization

n-Butylacrylate/acrylic acid (nBA/AA) copolymers were synthesized and used to modify epoxy resin (DGEBA) cured with dicyandiamide (DICY). The precuring reaction between nBA/AA copolymer and DGEBA, the curing cycle of DGEBA, and the effects of DICY and aluminum powder upon the adhesive strengths of modified DGEBA were studied. It was found that the optimum DICY/DGEBA ratio was 6 g/100 g, and lap shear strength and T-peel strength increased with increasing amount of aluminum powder. The curing cycle for modified DGEBA was determined to be 1 h at 177°C.     

Study on reaction kinetics of epoxy resin cured by a modified dicyandiamide

To improve the disadvantage of the low reactivity and reduce the high curing temperature of epoxy resin cured by dicyandiamide (DICY), DICY is chemically modified with phenyl hydrazine and a new curing agent, LB‐A, is developed in this research. The structure, the curing behavior, and reaction kinetics of LB‐A curing epoxy resin are investigated. Results show that the DICY is modified successfully and the well‐defined structure of DICY is destroyed after modification. Consequently, a new curing agent in a noncrystal form is resulted. Thereupon, the reactivity and compatibility between the epoxy resin and the curing agent are improved appreciably using LB‐A instead of DICY. Meanwhile, the curing temperature and activation energy of the curing reaction decrease outstanding, whereas the rate constant increases remarkably. In addition, the compressive strength and the adhesive strength in shear by tension loading of the resulting epoxy resins have been increased using LB‐A instead of DICY as the curing agent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Curing behavior of liquid crystalline epoxy/DGEBA blend

The effect of liquid crystalline epoxy (LCE) resin on the curing behavior and thermomechanical properties of diglycidylether of bisphenol A (DGEBA) was investigated. LCE was blended with DGEBA and curing behavior of the blend was studied according to LCE content in the blend. Curing of DGEBA was accelerated and thermomechanical properties of DGEBA were considerably improved by the addition of LCE, which acted as a molecular reinforcement. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Application of a new modified epoxy adhesive for bonding fluorine rubber to metal

Adhesion of fluorine rubber to metals is an important issue. The aim of this work was to develop a new kind of adhesive for bonding fluorine rubber to metals. A new modified epoxy adhesive containing a special tackifier resin obtained from polysulfones with a high heat deflection temperature (HDT) was prepared. Study on the curing behavior of the adhesive was carried out. Properties of the adhesive and the effects of several main factors were studied by gelation time test, differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. The optimum amount of the tackifier resin was found to be 50 phr; the average tensile lap shear strength could be achieved to a level of 8–10 MPa. Infrared attenuated total reflection (IRATR) spectroscopy indicated that the tackifier resin accelerated the establishment of epoxy resin adhesion to steel, and also promoted bonding and vulcanization of fluorine rubber. Easy diffusion of cyanamide (decomposition compound of dicyandiamide (DICY) in the curing process) into epoxy resin and fluorine rubber facilitated the dissolution and reaction of DICY, and also promoted formation of complex bond between fluorine rubber and adhesive, hence an enhanced adhesion of fluorine rubber to metal was achieved.     

聚双胍/环氧树脂体系潜伏性固化过程

用己二胺与双氰胺熔融缩聚, 合成了一种新型潜伏性环氧树脂固化剂, 并研究了其与环氧树脂的固化过程。用FTIR、XPS、¹H NMR分析了固化剂的结构;用DSC分析得到了固化剂与环氧树脂的适宜配比、固化体系的适宜固化温度及固化动力学参数;通过XRD分析了固化物的相结构;通过TG分析了固化物的热稳定性。结果表明, 与双氰胺环氧树脂固化体系相比, 固化温度降低近70℃, 同时潜伏性能良好, 30 d内固化度少于10%, 热稳定性能良好, 热分解温度超过300℃。     

Cure monitoring of epoxy films by heatable in situ FTIR analysis: correlation to composite parts

The curing mechanism of an epoxy film containing dicyandiamide (DICY) and an epoxy formulation based on diglycidyl ether of Bisphenol A (DGEBA) polymer was studied as a function of various temperature programs. The investigation was performed in situ, using a thin film of the epoxy mixture on a silicon wafer substrate in a heatable transmission tool of a FTIR spectrometer. Based on these model‐curing experiments, a major curing mechanism was proposed, taking into account the appearance, the decrease, and the development of characteristic bands at various temperatures. The conclusions of the model curing were correlated to FTIR measurements on a real, 50‐mm‐thick glass fiber reinforced component composite part from a technical process. It could be shown that characteristic bands that develop at curing temperatures above 150°C appear especially in the center of the thick sample. From the chemical or molecular point of view, this demonstrates the established technician's understanding that temperature control inside a large‐scale fiber composite of, for example, aircraft, wind‐turbine, automotive applications component is of major importance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39832.     

Matrix–particle interactions in catalyzed and uncatalyzed copper-filled epoxy matrix composites

Epoxy composites filled with copper particles with sizes of the order of 100 μm are studied with the aim of analyzing the particle–matrix interphase. Two matrixes are used: diglycidyl ether of bisphenol A resin (DGEBA)–anhydride catalyzed using a tertiary amine, and uncatalyzed DGEBA–anhydride. The surface of both types of composites was analyzed using scanning electron microscopy, X-ray photoelectron spectroscopy, and instrumented nanoindentation. The formation of Cu(I) and Cu(II) complexes is revealed using X-ray photoelectron spectroscopy, while instrumented nanoindentation measurements allow us to determine regions with different mechanical properties in the uncatalyzed composite. The influence of anhydride and the type of curing reaction on the formation of copper complexes is analyzed. The main results point out that copper particles can interact strongly with the epoxy, depending on the chemistry and kinetics of the curing reaction, to modify the composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47511.     

新型潜伏性固化剂的合成及性能

利用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）的亲核特点,将其与双氰胺进行加成反应,合成了一种潜伏性固化剂,并将其与环氧树脂进行固化反应。用FTIR、¹H NMR分析了固化剂的结构;用DSC、TG分析了固化剂和固化体系的热性能。结果表明,与双氰胺相比,固化剂的熔点降低了近100℃,固化温度下降近 40℃;优化了固化工艺参数;考察了体系的潜伏性和难燃特性,其储存期超过100 d,LOI达到22。     

改性双氰胺衍生物环氧固化剂的制备及性能研究

分别采用环氧丙烷、环氧丙烷丁基醚(501)和环氧树脂(EP)对双氰胺(DICY)进行改性,制备了一系列新型的改性DICY衍生物作为EP固化剂,并对改性DICY/EP固化体系的性能进行了初步研究。结果表明:当反应温度为95～105℃、n(DICY)∶n(环氧丙烷)=1∶1.1和n(DICY)∶n(501)=1∶1.3时,环氧丙烷改性DICY(反应3.0 h左右)和501改性DICY(反应3.0～4.0 h)的收率较高;EP改性DICY的最佳反应条件为反应温度105℃左右、反应时间4.0 h左右和n(DICY)∶n(EP)=1∶1.3。环氧丙烷(或501)改性DICY在室温时具有一定的潜伏性,与EP的相容性得到明显改善,并且其固化体系的起始放热温度比DICY体系降低了近40℃(或30℃);EP改性DICY具有较好的潜伏性(与DICY相当),并且极易溶于EP中,但其固化体系的起始放热温度稍低于DICY体系。     

咪唑促进双氰胺固化环氧树脂体系固化动力学

采用差示扫描量热(DSC)法研究了2-乙基-4-甲基咪唑(2E4MI)的含量对双氰胺(DICY)固化环氧树脂体系固化动力学的影响。非等温DSC测试结果表明,2E4MI能大幅度降低DICY固化环氧树脂所需要的温度和活化能,从而加快反应的进行。当2E4MI用量为0.2份时,活化能最低为84.2 kJ/mol且整体活化能随固化度的变化较小、固化更均匀。在2E4MI最佳用量(0.2份)下对固化体系进行等温DSC以及潜伏性测试,结果表明,该体系在160℃下20 min内可完成固化,室温储存15 d的固化度仅为0.146,说明其适合用作快速固化环氧树脂储存体系。     

Preparation and properties of heat and ultraviolet‐induced bonding and debonding epoxy/epoxy acrylate adhesives

Heat and ultraviolet (UV)‐induced bonding and debonding (BDB) adhesives were designed and prepared through blending an epoxy resin, diglycidyl ether of bisphenol A (DGEBA) with an epoxy acrylate resin, bisphenol‐A epoxy acrylate resin (BEA). The variation of the chemical structure of DGEBA and BEA in the sequential heat‐ and UV‐curing processes was characterized by Fourier transform infrared spectroscopy (FTIR). The FTIR results indicate that DGEBA and BEA successfully took part in both the heat‐curing and UV‐curing processes. The effects of the mass ratio of BEA to DGEBA, amount of heat‐curing agent, type of diluents, and UV irradiation time on the BDB properties of BDB adhesive were systematically investigated. The results show that the bonding strength increases with the decrease of the mass ratio of BEA to DGEBA and with the increase of the amount of heat‐curing agent in a certain range. The debonding strength decreases with the increase of the mass ratio of BEA to DGEBA. The mass ratio of BEA to DGEBA was set at 10 to ensure the ratio of the bonding strength to debonding strength greater than 10 times. The debonding strength of BDB adhesives also depends on the UV irradiation time, decreasing with the increase of UV irradiation time in a certain range. Based on the FTIR results and the dependence of the bonding and deboning strengths on the reaction conditions, a possible BDB mechanism of BDB adhesive was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46435.     

Novel adamantane‐containing epoxy resin

A novel adamantane‐containing epoxy resin diglycidyl ether of bisphenol‐adamantane (DGEBAda) was successfully synthesized from 1,3‐bis(4‐hydroxyphenyl)adamantane by a one‐step method. The proposed structure of the epoxy resin was confirmed with Fourier transform infrared, ¹H‐NMR, gel permeation chromatography, and epoxy equivalent weight titration. The synthesized adamantane‐containing epoxy resin was cured with 4,4′‐diaminodiphenyl sulfone (DDS) and dicyandiamide (DICY). The thermal properties of the DDS‐cured epoxy were investigated with differential scanning calorimetry and thermogravimetric analysis (TGA). The dielectric properties of the DICY‐cured epoxy were determined from its dielectric spectrum. The obtained results were compared with those of commercially available diglycidyl ether of bisphenol A (DGEBA), a tetramethyl biphenol (TMBP)/epoxy system, and some other associated epoxy resins. According to the measured values, the glass‐transition temperature of the DGEBAda/DDS system (223°C) was higher than that of the DGEBA/DDS system and close to that of the TMBP/DDS system. TGA results showed that the DGEBAda/DDS system had a higher char yield (25.02%) and integral procedure decomposition temperature (850.7°C); however, the 5 wt % degradation temperature was lower than that of DDS‐cured DGEBA and TMBP. Moreover, DGEBAda/DDS had reduced moisture absorption and lower dielectric properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study on Novel Epoxy Based Poly (Schiff Reagent)s

Abstract

Novel poly(schiff reagent)s from diketo derivative of epoxy resin were synthesised and characterised. A series of epoxy resin based poly(schiff reagent)s were synthesised by reacting an epoxy resin, diglycidyl ether of bisphenol-A (DGEBA) with 4-amino acetophenone (4-AAP) in a 1:2 mole ratio to afford the corresponding diketo derivative, and subsequent reaction with various aliphatic diamines in a presence of a triethyl amino as a catalyst. The resultant poly(schiff reagent)s were characterised by infrared spectroscopy (IR) and number average molecular weight (Mn) of PSs were estimated by non-aqueous conductometric titration. As produced, PSs having amine groups may act for curing of epoxy resins. Differential scanning calorimetric (DSC) curing kinetics of the epoxy resins viz. diglycidyl ether of bisphenol-A(DGEBA) and triglytidyl-p-amino phenol (TGPAP) have been investigated using PSs as a curing agent and triethyl amine as a catalyst. Thermal stability of the cured epoxy systems were studied by thermogravimetric analysis (TGA). The glass fiber reinforced composites of the produced PSs-epoxy system have been fabricated and were characterised by their mechanical properties and chemical resistance.     

两种典型环氧树脂基覆铜板加工工艺的对比研究

采用差示扫描量热仪和旋转流变仪对比研究了双氰胺(DICY)/环氧树脂和酚醛树脂(PN)/环氧树脂两种典型的环氧树脂基覆铜板用环氧树脂体系的固化行为和流变特性,求出了固化动力学参数,同时考察了填料对PN/环氧树脂固化体系流变特性的影响,优化了层压工艺参数.     

Phase Separation of Poly(ether sulfone imide) Modified Epoxy Resins

Amine terminated poly(ether sulfone imide) (PESI) with various imide and ethersulfone contents but similar polymer molecular weights were blended with diglycidyletherbisphenol-A (DGEBA) and cured with diaminodiphenylsulfone (DDS). The imide group, a tertiary amine, is a catalyst of the curing reaction of DGEBA with DDS, but it is poorly compatible with uncured epoxy resin. The ethersulfone group is not a catalyst of the curing reaction of DGEBA with DDS, but it has a similar chemical structure as DDS and is compatible with epoxy resin while it is at a low degree of curing. Since PESIs used in this study had similar molecular weights, increasing imide content of PESI would reduce ethersulfone content. The influence of imide and ethersulfone contents of PESI on the phase separation and curing reaction of DGEBA/DDS/PESI blend was investigated using differential scanning calorimetry (DSC), time-resolved light scattering (TRLS), and polarized optical microscopy (POM). Though the imide group has a catalysis effect on the curing reaction of DGEBA with DDS, however, its poor compatibility with epoxy resin retards the curing reaction. Our experimental results revealed the morphology of the cured blends and the curing behavior was a compromise result of catalysis and compatibility of PESI with epoxy resin.     

Confocal microscopy study of phase morphology evolution in epoxy/polysiloxane thermosets

The morphology of stoichiometric initially immiscible reactive blends of DGEBA epoxy resin and poly(3-aminopropylmethylsiloxane) has been characterized by laser scanning confocal microscopy. Observations were done on samples cured isothermally at different curing temperatures in the range 20-120 °C as well as in situ and in real time at 60 °C. Three different processes were revealed: coalescence, which occurs primarily at very low conversion, diffusion of DGEBA through polysiloxane-rich domains and chemical reaction, which occurs at the interphase between both phases. The interphase-thickness and compositional gradients were characterized by laser scanning confocal microscopy (LSCM). Results show that as curing temperature increases within the studied range, the material becomes more homogeneous although the interphase thickness remains almost constant.     

Interactions between silica nanoparticles and an epoxy resin before and during network formation

In polymer nanocomposites, interactions between filler particles and matrix material play a crucial role for their macroscopic properties. Nanocomposites consisting of varying amounts of silica nanoparticles and an epoxy resin based on diglycidyl ether of bisphenol-A (DGEBA) have been studied before and during network formation (curing). Rheology and mainly temperature modulated differential scanning calorimetry (TMDSC) have been used to investigate interactions between the silica nanoparticles and molecules of the epoxy oligomer or molecules of the growing epoxy network. Measurements of the complex specific heat capacity before curing showed that interactions between the nanoparticles and DGEBA molecules are very weak. An expression for an effective specific heat capacity of the silica nanoparticles could be deduced. Examination of the isothermal curing process after addition of an amine hardener yielded evidences for a restricted molecular mobility of the reactants in the cause of network formation. These restrictions could be overcome by increasing the curing temperature. No evidences for an incorporation of the silica nanoparticles into the epoxy network, i.e. for a strong chemical bonding to the network, were found. Interactions between the silica nanoparticles and the epoxy resins under study are assumed to be of a physical nature at all stages of network formation.     

Influence of rubber on the curing kinetics of DGEBA epoxy and the effect on the morphology and hardness of the composites

The influence of the end groups of two liquid rubbers on curing kinetics, morphology, and hardness behavior of diglycidyl ether of bisphenol-A based epoxy resin (DGEBA) has been studied. The rubbers are silyl-dihydroxy terminated (PDMS-co-DPS-OH) and silyl-diglycidyl ether terminated (PDMS-DGE). Crosslinking reactions, investigated by shear rheometry, ranged 90–110 °C, using a constant concentration (5 phr) of liquid rubbers and 1,2-Diamino cyclohexane (1,2-DCH) as hardener agent. The gel time, t _gel, of the neat epoxy significantly decreased when adding the elastomers, more so for the silyl-dihydroxy terminated elastomer; at 110 °C the reaction was nearly complete before rheological test started. The results suggest that the elastomers induced a catalytic effect on the curing reaction. Scanning electron microscopy revealed phase separation of the elastomer during the curing reaction with rubber domains about 5 μm size. However, the DGEBA/dihydroxy terminated elastomer composite cured at 110 °C exhibited a homogenous morphology, that is, the rapid reaction time would not allow for phase separation. Water contact angle tests evidenced either more hydrophilic (silyl-diglycidyl ether terminated rubber) or more hydrophobic (silyl-dihydroxy terminated rubber) behavior than the neat epoxy. The latter effect is attributed to the presence of aromatic rings in the backbone structure of PDMS-co-DPS-OH. Microindentation measurements show that the elastomers significantly reduced the hardness of the epoxy resin, the DGEBA/ether terminated composite exhibiting the lowest hardness values. Moreover, hardness increased as reaction temperature did, correlating with a reduction of microdomains size thus enabling the tuning of mechanical properties with reaction temperature.     

Study on Novel Epoxy Based Poly(schiff reagent)s

Abstract

Novel poly(schiff reagent)s (PSs) from diketo derivative of epoxy resin were synthesised and characterised. A series of epoxy resin based poly(schiff reagent)s were synthesised by reacting an epoxy resin, diglycidyl ether of bisphenol-A (DGEBA) with 4-amino acetophenone (4-AAP) in a 1:2 mole ratio to afford the corresponding diketo derivative, and subsequent reaction with various aliphatic diamines in the presence of a triethyl amine as a catalyst The resultant poly(schiff reagent)s were characterised by infrared spectroscopy (IR) and number average molecular weight (Mn) of PSs were estimated by non-aqueous conductometric titration. As produced, PSs having amine groups may act for curing of epoxy resins. Differential scanning calorimetric (DSC) curing kinetics of the epoxy resins viz., diglycidyl ether of bisphenol-A(DGEBA) and triglycidyl-p-amino phenol (TGPAP) have been investigated using PSs as a curing agent and triethyl amine as a catalyst. Thermal stability of the cured epoxy systems was studied by thermo-gravimetric analysis (TGA). The glass fiber reinforced composites of the produced PSs-epoxy system have been fabricated and were characterised by their mechanical properties and chemical resistance.     

Preparation of a light color cardanol-based curing agent and epoxy resin composite: Cure-induced phase separation and its effect on properties

A light color cardanol-based epoxy curing agent (MBCBE) was synthesized from cardanol butyl ether, formaldehyde and diethylenetriamine. In comparison, a phenalkamine with a similar structure was also prepared. The chemical structures were confirmed by GC–MS and FTIR. The cure behaviors of diglycidyl ether of bisphenol A (DGEBA) with these two curing agents was studied by differential scanning calorimetry (DSC). The morphology, mechanical properties, thermal properties of the cured epoxies were also investigated. The DSC results indicated that MBCBE is less reactive than the phenalkamine. The morphology of the cured MBCBE/DGEBA consisted of cavities dispersed within a continuous epoxy matrix. The cavities markedly improved the lap shear strength and impact strength of the cured resin. Both the two cured resins indicated a two-stage decomposition mechanism. Compared with PKA/DGEBA, the weight loss of MBCBE/DGEBA at the first stage was mainly resulted from the dispersed phase in the epoxy matrix.