The development of canola oil based bio‐resins

Bio‐based resins made from vegetable oils offer a sustainable alternative to petroleum‐based thermoset resins. The thermosetting resin systems we have developed from epoxidized canola oil and the polyurethanes we have produced from canola oil‐based polyols show promise as cost‐effective materials incorporating a high renewable content. Here we outline the use of canola oil based bio‐resins in composite boards, and in polyurethane adhesive and insulating foam applications.     

Investigation of the effect of different silane coupling agents on mechanical performance of basalt fiber composite laminates with biobased epoxy matrices

In recent years, it has been detected an increased interest in the development of materials from renewable resources. This trend has been intensified in the industrial sector where significant efforts have been made in this field in order to adapt these natural fibers to conventional industrial processes and applications. As a result, research has been done into developing new thermoplastic matrices which are compatible with this type of reinforcing fibers. This study evaluates the influence of different coupling agents based on silanes, on the mechanical properties of composite laminates made from a biobased epoxy resin matrix and basalt fabric by using vacuum assisted resin transfer moulding. The curing behavior of the biobased epoxy resin was evaluated by differential scanning calorimetry (DSC), gel point determination, and ionic conductivity. The evaluation of mechanical properties was done by tensile, flexural, impact, and hardness tests. Compatibility between basalt fibers and epoxy resin generally has managed to increase through the addition of silanes, after the addition of these, their mechanical properties are substantially improved compared to the sample without silane treatment, obtaining this way an easily processable material, with good properties and capable of competing with materials with petroleum‐based epoxy resins. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of petroleum and biobased epoxy resins: a review

Petroleum based epoxy resins exhibit various excellent properties such as adhesion, mechanical performance, electrical insulation and chemical resistance. There is wide concern towards depletion of non‐renewable resources, climate change and finding renewable alternatives for petroleum based materials to reduce the emission of greenhouse gases. This review mainly draws attention towards the utilization of renewable resource based epoxy resin derived from lignocellulosic biomass, furan, tannins, itaconic acid, rosin acid and bio‐oil etc. Without altering the mechanical and thermal properties much, epoxy resins derived from renewable materials have been widely investigated. The last two decades have witnessed an exponential growth in using bio‐derived products, which has been driven by the need to replace petroleum based materials, reduce fuel consumption and lower the overall environmental impact. © 2018 Society of Chemical Industry     

Selected biotrends in development of epoxy resins and their composites

Epoxy resins and their fibre or particulate composites are widely used in various industries, including building, naval, aircraft, automotive and aerospace. Modern polymer science and technology focus on the development of green polymers and composites. There are two major areas of interest in the case of epoxy resins: the development of bio-based resins and the production of composites with natural fibres. One of the most interesting challenges is developing fully bio-based composites: that is, epoxy resins based on renewable resources and natural fibres. This paper presents a review of literature on epoxy resins and hardeners based on renewable resources (especially vegetable oils) and epoxy composites with natural fibres. We also describe some of the effective methods of improving the mechanical properties of epoxy–natural fibres composites, including chemical modification of the fibre surface and the application of hybrid reinforcements.     

Comparison of curing agents for epoxidized vegetable oils applied to composites

Interest in polymers from renewable sources, as alternatives to petroleum‐based polymers, remains strong; however, their performance must be acceptable. To improve performance of epoxidized vegetable oils (EVO) in composite matrix applications, five amine curing agents were evaluated and compared with an anhydride agent used previously. Curing agents were tested in matrices for composites containing a petroleum‐based epoxy resin plus 0% or 30% epoxidized oil from canola (ECO) and soybean (ESO). The two amines with the highest glass transition temperature, determined by differential scanning calorimetry, were selected for characterization by dynamic mechanical analysis; bis (p‐aminocyclohexyl) methane (PACM) showed the highest performance. Amine: epoxy ratios 0.6 to 1.6 were then evaluated; ratios of 0.8 and 1.0 showed superior performance. E‐glass fiber reinforced composites with PACM/EVO showed thermal and mechanical performance slightly lower than the composites with 0% EVO and comparable with those of the anhydride curing agent. Therefore, ECO or ESO blended with petroleum‐based epoxy resins cured with PACM are recommended for its application in E‐glass reinforced composites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Room temperature‐curable VARTM epoxy resins: Promising alternative to vinyl ester resins

The objective of this investigation is to characterize various room temperature (RT)‐curable epoxies for vacuum‐assisted resin transfer molding (VARTM) of large structure manufacturing. Six epoxy candidate resins: X‐40, 780‐33, 780‐35, 8601/8602, 8602, 8603, and two vinyl ester resins (VE), 411‐350 and 411‐510A, are physically and thermochemically characterized. All the resins are cured at RT with extended period of time. The degree of cure for 24‐h RT‐cured samples ranges from 70 to 85% for epoxies and is comparable with the baseline VE systems (75%). After 1 year at RT, the degree of cure increases from 90 to 98%. Most of the epoxies show a single transition in dynamic mechanical analysis and differential scanning calorimetry. However, two heterogeneous transitions are observed for the VE systems. The glass transition temperature increases monotonically with exposure time, except X‐40, that rapidly achieves a plateau and remains constant. The degree of cure for the majority of the systems increases logarithmically with RT curing time with excellent fitting (R² varies from 0.92 to 1). Consistent with the increase in degree of cure, the storage modulus increases and (tan δ)_max decreases with time of exposure. A negative correlation between the curing temperature range and the total heat of reaction is observed among the epoxy systems. However, the VE systems show the reverse trend. RT curing epoxy resin (X‐40) shows promising overall result to VE system and can be a viable alternative to VE for VARTM processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

环氧树脂聚酰胺网络体系性能研究

用红外光谱法表征了4种聚酰胺固化剂与环氧树脂按等当量配比,在一定条件下的固化反应过程。DSC法测定了其固化反应活性。桐马聚酰胺/环氧树脂固化体系较聚酰胺650/环氧树脂固化体系的固化活性大大提高,同时测定了该固化产物的热失重(TG)及玻璃化温度(Tg),对该固化物的热稳定性进行了评价,还测定了不同固化时间的剪切强度以研究其动态力学性能,从浇铸体的冲击强度方面比较其韧性。综合比较分析了聚酰胺固化剂与环氧树脂固化体系的力学性能、耐热性、电绝缘性等。结果表明:桐马聚酰胺Ⅲ型固化剂具有黏度低、粘接强度大、耐热性好、力学性能优等优点。     

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.     

Multifunctional formaldehyde resins as curing agent for epoxy resins

Formaldehyde resins (FR) at 1/1/2 molar ratios of monomers (Cl‐phenol/amino monomers/p‐formaldehyde) were synthesized under acid catalysis. The obtained resins were characterized using elemental analysis, FTIR and RMN spectroscopic methods, being used as crosslinking agents for epoxy resin formulations. The curing of epoxy resins with FR were investigated. The glass transition temperature (T_g) and decomposition behavior of crosslinked resins were studied by differential scanning calorimetry (DSC) and thermogravimetric (TGA) techniques. All DSC scans show two exothermic peaks, which implied the occurrence of cure reactions between epoxy ring and amine or carboxylic protons, in function of chemical structures of FR. The crosslinked products showed good thermal properties, high glass transitions, and low water absorption. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High temperature vacuum assisted resin transfer molding of phenylethynyl terminated imide composites

Vacuum Assisted Resin Transfer Molding (VARTM) has proven to be a cost effective process for manufacturing composite structures compared with prepreg/autoclave and traditional resin transfer molding (RTM) processes. However, VARTM has not been accomplished with high temperature resins (such as polyimides) until recently, primarily because no resins had low melt viscosity and long melt stability that are required by VARTM. With the recent invention of phenylethynyl terminated imides (PETIs), high temperature VARTM has been achieved. Two processing methods, in‐plane and through‐thickness resin flow, were proposed and tested. Both methods are capable of fabricating polyimide matrix composites; and the carbon fiber laminates yield good fiber‐resin interfacial bonding and comparable mechanical properties to those laminates fabricated using RTM. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Synthesis of epoxy resins from alcohol‐liquefied wood and the mechanical properties of the cured resins

New wood‐based epoxy resins were synthesized from alcohol‐liquefied wood. Wood was first liquefied by the reaction with polyethylene glycol and glycerin. The alcohol‐liquefied wood with plenty of hydroxyl groups were precursors for synthesizing the wood‐based epoxy resins. Namely, the alcoholic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition with a phase transfer catalyst, so that the epoxy groups were put in the liquefied wood. The wood‐based epoxy resins and the alcohol‐based epoxy resins as reference materials were cured with polyamide amine. The glass transition temperature (Tg), the tensile strength, and the modulus of elasticity of the wood‐based epoxy resin were higher than those of the alcohol‐based epoxy resin. Also, the shear adhesive strength of the wood‐based epoxy resin to steel plates was higher than those of the alcohol‐based epoxy resins, which was equivalent to the level of petroleum‐based bisphenol‐A type epoxy resins. The higher Tg of the wood‐based epoxy resin than that of the alcohol‐based epoxy resin is one of the evidences that the wood‐derived molecules were chemically incorporated into the network structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

高性能环氧树脂基体的发展

综述了高性能环氧树脂的制备方法和性能。介绍了几种高性能的环氧树脂固化体系 ,新型的耐湿热性的环氧树脂 ,氰酸酯改性环氧树脂 ,液晶环氧树脂 ,双马来酰亚胺改性环氧树脂等     

Biolignin™ based epoxy resins

Wheat straw Biolignin? was used as a substitute of bisphenol‐A in epoxy resin. Synthesis was carried out in alkaline aqueous media using polyethyleneglycol diglycidyl ether (PEGDGE) as epoxide agent. Structural study of Biolignin? and PEGDGE was performed by solid‐state ¹³C NMR and gel permeation chromatography, respectively, before epoxy resin synthesis. Biolignin? based epoxy resins were obtained with different ratios of Biolignin? : PEGDGE and their structures were analyzed by solid‐state ¹³C NMR. The crosslinking of PEGDGE with Biolignin? was highlighted in this study. Properties of Biolignin? based epoxy resins were analyzed by differential scanning calorimetry and dynamic load thermomechanical analysis as well as compared with those of a bisphenol‐A epoxy‐amine resin. Depending on the epoxy resin formulation, results confirmed the high potential of Biolignin? as a biosourced polyphenol used in epoxy resin applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reactive blending of functionalized acrylic rubbers and epoxy resins

A high molecular weight acrylonitrile/butadiene/methacrylic acid (Nipol 1472) rubber is chosen to control processability and mechanical properties of a TGDDM (tetra glycidyl diphenyl methane) based epoxy resin formulation for aerospace composite applications. The physical blend of rubber and epoxy resin, achieved by dissolution of all the components in a common solvent, forms a heterogeneous system after solvent removal and presents coarse phase separation during cure that impairs any practical relevance of this material. A marked improvement of rubberepoxy miscibility is achieved by reactive blending (‘pre‐reaction’) the epoxy oligomer with the functional groups present in the rubber. The epoxy‐rubber ‘adduct’ so obtained appears as a homogeneous system at room temperature and also after compounding with the curing agent. Depending on the nature and extent of interactions developed between the rubber and the epoxy resin during ‘pre‐reaction,’ materials with different resin flow characteristics, distinctive morphologies and mechanical properties after curing were obtained. The effect of ‘pre‐reaction’ on the resin cure reaction kinetics has been also investigated.     

Toughening of epoxy resins by modified m-phenylene diamine having soft ether chain

A new soften curing agent for toughening epoxy resins was synthesized by m-phenylene diamine modified with epoxypropyl butyl ether. The curing processes of epoxy resin/modified m-phenylene diamine were traced by differential scanning calorimetry (DSC), then kinetic parameters, ΔE and n, were deduced. Fourier transform infrared (FTIR) analysis showed that the longer the reaction time was, the smaller the absorption peaks of epoxy group were. The results of the mechanical properties demonstrated that the impact property of the epoxy resin cured by modified m-phenylene diamine at the moderate temperature was better than that of cured by unmodified one because of the introduction of soft ether chain. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New biobased carboxylic acid hardeners for epoxy resins

Soybean oil was modified into a novel biobased polyacid hardener by thiol‐ene coupling with thioglycolic acid. The structure of the initial soybean oil and polyacid triglyceride was carefully analyzed using ¹H NMR and titration. The thermal crosslinking reaction between acid hardener and epoxidized resin was studied by differential scanning calorimetry (DSC) and rheology. Then, the synthesized biobased acid hardener was employed as a novel curing agent for bisphenol A diglycidyl ether to elaborate new partially biobased materials. These materials, formulated in stoichiometry ratio, were characterized by DSC, thermogravimetry analyses, dynamic mechanical analyses and exhibit interesting properties for coatings. Practical applications: The products of the chemistry described in this contribution, i.e., polyacid from soybean oil and thioglycolic acid, provide biobased building blocks for further epoxy resin syntheses by reaction with epoxy groups. The obtained epoxy resins are partially biobased and may be applied as binders and coatings.     

Effect of prereaction on curing of elastomer-modified epoxy resins

Three multifunctional epoxy resins novolac epoxy (EPN), triglycidyl para-aminophenol (TGPAP), and tetraglycidyl diaminodiphenylmethane (TGDDM) were modified with a carboxy-terminated acrylate-based liquid elastomer (PnBA). The effect of prereaction of the epoxy groups in the resin and carboxyl group in the elastomer on curing parameters, such as the cure reaction conversions; processing parameters, such as gel times and vetrification times; initial cure temperatures, and activation energy values were evaluated. Fourier transform infrared spectrometry (FTIR), dynamic mechanical spectrometry (DMS), and differential scanning calorimetry (DSC) were used for the study. The results indicated that while the cure reactions were slightly retarded in the presence of elastomer, they were slightly accelerated when certain prereaction catalysts were used. The gel times and vitrification times decreased due to the prereaction. The physical properties such as fracture toughness and modulus of neat resin castings and flexural strength properties of carbon cloth-reinforced laminates were evaluated. Results indicated that the toughness property increased and the modulus decreased with elastomer addition. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1751–1757, 1997     

Addition of polyethersulphone to epoxy resins

Phase separation of polyethersulphone from solution in epoxy resins has been studied as a function of polyethersulphone concentration, type of resin, and curing conditions. The resins chosen were a rapidly curing tetrafunctional and a trifunctional epoxy resin, hardened with either diaminodiphenylsulphone, or dicyandiamide. Fracture surfaces of some of the cured blends exhibited nodular features between 0.2μm and 6μm in diameter. Using X-ray microanalysis and scanning electron microscopy these nodules were shown to contain high concentrations of polyethersulphone. Mechanical properties, including fracture energy, dynamic mechanical relaxation and creep, were studied for the same range of blend compositions. Dynamic mechanical spectra provided further evidence for phase separation in certain blends, while elastic modulus, fracture toughness and creep showed little dependence upon composition.     

双邻苯二甲腈改性环氧及其玻纤复合材料制备

采用双邻苯二甲腈树脂(BAPh)对环氧树脂E-44(EP)进行改性,同时制备了BAPh/EP/玻纤复合材料。采用示差扫描量热仪,热重分析,力学性能测试及氧指数仪研究了改性树脂的热性能、力学性能及阻燃性能,并对BAPh/EP/玻纤复合材料的力学性能进行了表征。结果表明,当BAPh质量分数达到50%时,改性树脂固化物在空气中的起始分解温度达到377.6℃,比纯环氧提高74.3℃,氧指数达到34.5%,复合材料的弯曲性能指标达到最大,添加双邻苯二甲腈后环氧树脂的耐热性、力学性能和阻燃性能得到了明显改善。     

Fracture and mechanical properties of epoxy resins and rubber-modified epoxy resins

Fracture and mechanical property data on a wide range of epoxy resin systems are presented. The extent to which toughening can be induced by heterophase rubber inclusions depends more on the curing agent used than on the resin component. The greatest improvements in toughness were obtained by rubber modification of epoxy resins cured with an anhydride. A preformed ABS polymer can be used to toughen many epoxy resin systems. With one major exception (where a large improvement was found) only small changes in tensile properties occur when small amounts of rubber are present.