Dynamic mechanical and thermal behavior of epoxy resins based on soybean oil

Mechanical and thermal properties of materials prepared by curing epoxidized soybean oil with various cyclic acid anhydrides in the presence of tertiary amines were investigated by dynamic mechanical thermal analysis and thermogravimetry. All samples presented thermoset material characteristics that were dependent upon the type of anhydride, the anhydride/epoxy molar ratio, and epoxy group content. The thermosets obtained from anhydrides with rigid structures as such phthalic, maleic, and hexahydrophthalic showed higher glass transition temperatures (Tg) and cross-linking densities. As expected, the Tg decreased as the anhydride/epoxy ratio decreased. The influence of the degree of epoxidation of soybean oil on the mechanical properties and Tg was also investigated. It was found that the higher the epoxy group amount, the higher the Tg and hardness. Cured resins exhibited thermal stability up to 300°C, except for those prepared with dodecenyl succinic anhydride, which began to decompose at lower temperature. They presented excellent chemical resistance when immersed in 1% wt/vol NaOH and 3% wt/vol H₂SO₄ solutions but poor chemical resistance in the presence of organic solvents.     

环氧树脂复合泡沫材料的制备研究

以缩水甘油酯环氧树脂(EP)、酸酐固化剂和空心玻璃微珠为主要原料,通过添加一定的活性稀释剂,高温固化制备了EP复合泡沫材料。研究了空心玻璃微珠的表面改性对复合泡沫材料性能的影响。结果表明,复合泡沫材料性能与空心玻璃微珠的表面性能密切相关,当EP/固化剂/稀释剂的质量比为100/120/15、KH-560改性的空心玻璃微珠用量为30份时,所制备的复合泡沫材料密度为0.826 g/cm3,压缩强度达115.8 MPa,比强度为140.2。     

Bio-based Epoxy Resins from Epoxidized Plant Oils and Their Shape Memory Behaviors

In this study, bio‐based epoxy materials containing functionalized plant oil, such as epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO), were processed with 4‐methylhexahydrophthalic anhydride (MHPA) as a curing agent. In the presence of tetraethylammonium bromide, the curing reaction of epoxidized plant oil and MHPA proceeded at 130 °C to give transparent plant oil‐based epoxy materials. The resulting bio‐based epoxy materials exhibited relatively soft and flexible characters, due to the aliphatic chains of plant oil. The thermal and mechanical properties of the ESO/MHPA polymers depended on the feed molar ratio of anhydride to oxirane. The mechanical properties such as tensile strength and Young's modulus of the ELO/MHPA polymer increased, compared with those of the ESO/MHPA polymer. The glass transition temperature of the ELO/MHPA polymer was higher than that of the ESO/MHPA polymer, because of the high oxirane number of ELO. Furthermore, the ELO/MHPA polymer showed excellent shape memory property.     

Synthesis of rosin‐based flexible anhydride‐type curing agents and properties of the cured epoxy

BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using ¹H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry     

反应型E-31环氧树脂的制备与应用

本文叙述了缩聚反应制备E－31型环氧树脂的过程，通过改变原料配比及催化剂的浓度制得产品。介绍了中试产品的质量及在亚胺改性桐油酸酐环氧胶中使用性能．     

由苧烯合成脂环族双环氧化合物及固化物热性能

以天然产物(R)-(+)-苧烯为原料,通过烯烃加氢烷基化、酯化和有机过氧化物环氧化反应合成得到含有苧烯结构单元的新型双官能团脂环族环氧化合物。利用核磁共振波谱(1HNMR和13CNMR)、质谱和红外光谱(FTIR)来表征反应中间体和脂环族环氧化合物结构。以2-乙基-4-甲基咪唑为促进剂、酸酐为固化剂,采用示差扫描量热(DSC)和热重分析(TGA)方法研究该脂环族环氧固化物的热性能。环氧化合物与甲基六氢邻苯二甲酸酐、4-环己烯-1,2-二甲酸酐和内亚甲基邻苯二甲酸酐固化产物的Tg分别为158、137、150℃。结果表明,脂环族环氧化合物与酸酐固化剂热固化后得到的交联聚合物具有良好的热性能。     

A study by Raman, near-infrared and dynamic-mechanical spectroscopies on the curing behaviour, molecular structure and viscoelastic properties of epoxy/anhydride networks

The curing characteristics of a TGDDM/HHPA formulation have been investigated by Raman spectroscopy, which allowed us to monitor the evolution of the different reactive species (i.e. epoxy, anhydride and ester groups) participating in the curing process. The curing mechanism and, in particular, the role of side processes, were elucidated. NIR spectroscopy was employed to investigate the post-curing process, in view of the superior sensitivity of this technique for monitoring polar groups. Quantitative methods were developed to measure residual concentration of epoxy groups in the high conversion regimes (≥98%). Dynamic-mechanical measurements were performed to gather information on the molecular structure and viscoelastic properties of the investigated networks. For formulation rich in epoxy resin, clear evidence of an inhomogeneous phase structure was found. A viscoelastic analysis in terms of the WLF approach demonstrated that both the free volume and the thermal expansion coefficient of the networks decrease by enhancing the anhydride/epoxy molar ratio.     

Properties of Biobased Epoxy Resins from Epoxidized Soybean Oil (ESBO) Cured with Maleic Anhydride (MA)

Epoxidized soybean oil (ESBO), obtained from a renewable resource was used in the production of thermoset resins. Samples of the ESBO were initially treated with maleic anhydride, equal mixture of catalyst (1,3-butanediol anhydrous and benzyldimethylamine) and the mixture was cured for 5?h at different temperatures. After the curing process, the ratio between the ESBO and the anhydride (ratio EEW:AEW) was evaluated in terms of the different mechanical properties produced using flexural, Shore D hardness and Charpy impact tests. The sample with the best mechanical properties was that with an EEW:AEW ratio of 1:1.0 which leads to best balanced behavior and this could be representative for the maximum crosslinking degree. Also, thermal characteristics were evaluated during the crosslinking process using differential scanning calorimetry, In addition, other thermal characteristics of the cured materials were obtained by determining the heat deflection temperature and the Vicat softening temperature. The coefficient of thermal expansion was determined using thermo-mechanical analysis. In accordance with the mechanical behavior, the best thermal properties were obtained for samples with an EEW:AEW ratio of 1:1.0. As a result of this work, a biologically based epoxy resin with good mechanical properties and flexibility was obtained.     

Use of eugenol and rosin as feedstocks for biobased epoxy resins and study of curing and performance properties

In this study, an epoxy based on eugenol and an anhydride curing agent based on rosin were prepared. Curing of the eugenol epoxy with a commercial anhydride curing agent and with the rosin‐derived anhydride curing agent was studied. For comparison, a commercial bisphenol A type epoxy, DER353, was also selected in the curing study. The syntheses of the eugenol epoxy and rosin anhydride were investigated and the chemical structures of the products and intermediates were characterized using ¹H NMR and Fourier transform infrared spectroscopies. Non‐isothermal curing of the eugenol epoxy with hexahydrophthalic anhydride and the rosin‐derived maleopimaric acid was studied using differential scanning calorimetry. Thermomechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetric analysis, respectively. Addition of 2‐ethyl‐4‐methylimidazole as catalyst greatly decreased the curing temperature and promoted the completion of cure reactions. The results suggest that the eugenol epoxy and the bisphenol A type epoxy have similar reactivity, dynamic mechanical properties and thermal stability. © 2013 Society of Chemical Industry     

马来海松酸酐的合成及其固化反应特性研究

松香与亲二烯体进行Diels-Alder反应合成了环氧树脂固化剂马来海松酸酐,利用傅里叶红外光谱仪(FT-IR)、热重分析仪(DTA)、拉力机等分析测试手段,对环氧树脂/马来海松酸酐体系固化产物的特性进行了研究。结果表明,环氧树脂/马来海松酸酐固化体系在100℃/2h、120℃/2h、150℃/5h、质量比为1:0.8的条件下可完全固化。固化产物的平均剪切强度17.3MPa,热分解温度可达371.5℃,与甲基四氢苯酐(Me-TH-PA)/环氧固化物相比,分别高3.74MPa,6.1℃。该产物可望在环氧树脂中高温固化领域得到广泛应用。     

Chemical modification of unsaturated polyesters influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers

In this study, the chemical modification of unsaturated polyesters and the influence of polyester's structure on thermal and viscoelastic properties have been presented. The structure of unsaturated polyesters obtained in polycondensation of cyclohex‐4‐ene‐1,2‐dicarboxylic anhydride (THPA), maleic anhydride and only one suitable symmetrical glycol: ethylene glycol or 1,4‐butanediol (BDO) or 1,6‐hexanediol has been modified by peracetic acid. The selective oxidation of unsaturated polyesters conducted in mild time and temperature conditions was a successful and effective method to prepare new materials/unsaturated epoxy polyesters/containing epoxy groups in cycloaliphatic rings and carbon–carbon double bonds in polyester chain. The unsaturated epoxy polyesters were capable of both copolymerization with vinyl monomer and polyaddition reactions with suitable curing agent. Therefore, they were successfully used as a component of low styrene content copolymers. As was confirmed by DSC, DMA, and TGA analyses, polyester's structure had significant influence on thermal and viscoelastic properties of styrene copolymers. The properties of styrene copolymers prepared from unsaturated epoxy polyesters were considerably better compared with those obtained for styrene copolymers from unsaturated polyesters.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Siloxane- and Imide-modified Epoxy Resin Cured with Siloxane-containing Dianhydride

Hydrosilylation of nadic anhydride by tetramethyldisiloxane yielded 5,5’-(1,1,3,3-tetramethyl-1,1,3,3-disiloxanediayl)-bis-norborane-2,3-dicarboxylic anhydride (I), which further reacted with 4-aminophenol to form N,N’-bis(4-hydroxyphenyl)-5,5’-(1,1,3,3-tetramethyl-1,1,3,3-disiloxanediallyl)-binorborane-2,3-dicarboximide (II) reacted with epichlorohydrin to form siloxane- and imide-modified epoxy (i.e. N,N’-diglycidylether-bis-(4-phenyl)-5,5’-(1,1,3,3-tetramethyl-1,1,3,3-disloxanediallyl)-bis-norborane-2,3-dicarboximide (III) (Scheme 1). Various equivalent ratios of III/I for 1/1, 1/0.8 and Bisphenol F epoxy (830LVP DIC Co.)/I for 1/1, 1/0.8 were prepared and cured to produce four crosslinked materials. Thermal and dynamic mechanical properties were measured with TMA and DMA. Kinetic analysis was studied with dynamic DSC, which revealed a relatively lower curing activation energy of III/I systems, because the tertiary amine on the imide group catalyzed the curing reaction. III/I system also indicated moderate Tg, storage modulus but higher loss modulus as compared with Bisphenol F epoxy/I systems. These phenomena were interpreted by the fact that the siloxane group in III toughened the crosslinked materials. In addition, photos of SEM, carbon-mapping-SEM, oxygen-mapping SEM and siloxane-mapping-SEM indicated all homogeneity of these materials.     

The effect of graft copolymers of maleic anhydride and epoxy resin on the mechanical properties and morphology of PP/ABS blends

In this work, maleic anhydride‐grafted polypropylene (PP‐g‐MAH) and maleic anhydride‐grafted poly(acrylonitrile‐butadiene‐styrene) (ABS‐g‐MAH) at 2 : 1 mass ratio were added as a compatibilizer in the PP/ABS blends. The compatibilizing effect was evaluated by adding the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ). The reaction in reactive extrusion, morphological structure, and properties of PP and ABS blends were investigated by using infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray spectrum, transmission electron microscope (TEM), dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC), and mechanical properties tests. The results showed that the compatibilizing effect was greatly improved because of the addition of the graft copolymers together with epoxy resin/imidazole curing agent (E51/2E4MZ) because the link structure of PP‐g‐MAH and ABS‐g‐MAH was formed by the reaction of anhydride group with epoxy group catalyzed by the imidazole. The size of the dispersed phase decreased dramatically, the interfacial adhesion between ABS particles and PP matrix was improved, and the tensile strength and flexural modulus of the PP/ABS blends increased further. The optimizing properties were obtained at 3 phr E51/2E4MZ. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40898.     

Synthesis,characterization, thermal,and viscoelastic properties of an unsaturated epoxy polyester cured with different hardeners

The chemical modification of the structure of the unsaturated polyester obtained in poly condensation process of 1,2,3,6‐tetrahydrophthalic anhydride, maleic anhydride, and ethylene glycol by well known conventional method of epoxidation with peracetic acid in mild conditions has been presented. The new material containing both epoxy groups and unsaturated double bonds in polyester chain was characterized by FTIR and ¹H NMR spectra. The prepared unsaturated epoxy polyester was suitable material for further chemical modification. Both epoxy groups and unsaturated double bonds can be used as cross‐linking sites. Curing behavior, thermal, and visco‐elastic properties of the unsaturated epoxy polyester cured with different hardeners: 1,2,3,6‐tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), and/or with vinyl monomer (styrene) using radical initiator—benzoyl peroxide (BPO) were studied by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), and dynamic mechanical analysis (DMA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physico‐mechanical,thermal, and coating properties of composite materials prepared with epoxy resin/steel slag

The interest in using different solid waste as reinforcement in polymer composite preparation has increased considerably in recent years. Slag is one of the inorganic waste materials obtained from ore processing. In this work, epoxy composites filled with different percentages of slag were prepared. Physico‐mechanical, thermal, and coating properties of these composites were determined depending on the amount of filler, type of hardener, and polyethylene glycol (PEG) addition. X‐ray diffraction (XRD) studies were carried out to examine the compatibility of the filler and epoxy resin and XRD results showed good compatibility between two materials. The results of mechanical testing illustrated that hardness of the epoxy composites containing anhydride was partially higher than with Epamine PC17 in contrast to elongation at break. The tensile strength and Young modulus decreased with increasing filler amount. When compared to neat epoxy resin, corrosion, and adhesion properties of the composites with filler addition did not change significantly. The highest water sorption values were obtained for the epoxy composites with PEG addition. The composites hardened by anhydride had better thermal stability than the composites including Epamine PC17. POLYM. COMPOS., 38:1974–1981, 2017. © 2015 Society of Plastics Engineers     

腰果酚基环氧树脂的合成及其性能研究

设计合成了一种腰果酚基环氧树脂。首先,以羟乙基腰果酚醚(HCE)和三氯氧磷(POCl3)为原料,利用亲核取代反应合成了一种具有三臂结构的预聚体(PT-HCE)。采用双氧水/甲酸的均相催化法对PT-HCE进行了环氧化,合成了磷酸三羟乙基腰果酚醚环氧树脂(EPT-HCE),同时探究了甲酸的投料比对环氧值的影响。结果表明:当双键与甲酸的物质的量比为1∶0.4时,环氧值能达到最高值0.18 mol/(100 g)。通过傅里叶变换红外光谱仪(FT-IR)、核磁共振波谱仪(NMR)对PT-HCE和EPT-HCE的结构进行了表征,证明了环氧树脂被成功合成。此后,利用所合成的树脂制备了热固化涂料,研究了酸酐含量等对涂层附着力、铅笔硬度和耐冲击性等性能的影响,还将EPT-HCE与双酚A型环氧树脂E51进行了复配。结果表明:相比于纯E51环氧树脂制备的涂层,加入EPT-HCE树脂后的涂层柔韧性得到了提高。     

Simultaneous cationic polymerization and esterification of epoxy/anhydride system in the presence of polyoxometalate catalyst

Polyoxometalate exhibits high catalytic performance for the simultaneous cationic polymerization and esterification of epoxy resin when anhydride is introduced as a co-hardener. The selective catalysis effect of polyoxometalate and the reaction mechanism was studied by differential scanning calorimetry (DSC), mid-infrared spectroscopy (MIR), near-infrared spectroscopy (NIR) and generalized two-dimensional correlation analysis. The cationic polymerization is the dominating reaction in neat epoxy systems. Increasing the amount of polyoxometalate and the polarity of the diluents fastens the curing rate of epoxy resin. Esterification was found to be the preferred reaction once anhydride was employed. When polyoxometalate was blocked by amine to form salt, it performs as an excellent catalyst for esterification in epoxy-anhydride systems. The epoxy materials catalyzed by polyoxometalate show quite good performance compared with ordinary epoxy resins. Moreover, thermal degradation analysis (TGA) shows that polyoxometalate could significantly decrease the thermal degradation temperatures of cured epoxy resins.     

Quaternary phosphonium compounds as latent accelerators for anhydride-cured epoxy resins. I. Latency and cure characteristics

Quaternary phosphonium compounds have been found to be extremely effective latent accelerators for anhydride-cured bisphenol A epoxy resins; at concentrations from 0.01% to 0.25%, fast gel times are found in the temperature range of 135°–200°C combined with very good storage properties at ambient temperatures. Using these materials as accelerators, it is possible to formulate long-life, one-component epoxy resins. From gel time data, Arrhenius plots were made for some of these phosphonium compounds, and results indicate low activation energy values of the order of 16.1 kcal/mole. Reaction mechanisms are proposed to explain the effectiveness of these phosphonium compounds as latent accelerators. The initiation mechanism probably involves the formation of hydrogen-bonded phosphonium–epoxy or phosphonium–anhydride complexes which rearrange on the application of heat to form activated species resulting in polymerization of the epoxy–anhydride components. The transfer of a proton from the phosphonium complex(es) to other epoxy or anhydride molecules would appear to be the rate-determining step in this initiation mechanism. Comparison of other well-known accelerators used for the anhydride cure of bisphenol A epoxy resins shows quaternary phosphonium compounds to be among the most effective accelerators disclosed to date.     

Development and characterization of phosphorus-containing siliconized epoxy resin coatings

The objective of the present work is the development and characterization of siliconized epoxy-phosphorus based bismaleimide coating systems using diglycidylether terminated poly (dimethylsiloxane) (DGTPDMS) and phosphorus-containing bismaleimide (PBMI) as chemical modifiers for epoxy resin. Phosphorus-containing diamine (DOPO-NH₂) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 4,4′-diaminobenzophenone (DABP), which was utilized in the preparation of phosphorus-containing bismaleimide (PBMI) with maleic anhydride. Siliconized epoxy prepolymer was prepared using epoxy resin and functionally terminated polydimethylsiloxane. The purity and structural conformation of these materials were ascertained from FTIR and NMR spectral studies. The prepared siliconized epoxy prepolymer was blended with varying percentages of PBMI using diaminodiphenylsulfone (DDS) and diaminodiphenylmethane (DDM) as curing agents. The siliconized epoxy and bismaleimide modified epoxy and siliconized epoxy coating materials were characterized by dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), heat distortion temperature (HDT) and Limiting oxygen index (LOI).     

Conducting epoxy networks modified with non‐covalently functionalized multi‐walled carbon nanotube with imidazolium‐based ionic liquid

Multi‐walled carbon nanotube (MWCNT) was non‐covalently functionalized with room‐temperature ionic liquid (IL), 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate and blended with epoxy pre‐polymer (ER) with the assistance of ultrasonication in the presence of acetone as a diluting medium. The ability of IL in improving the dispersion of MWCNT in epoxy pre‐polymer was evidenced by transmission optical microscopy. The corresponding epoxy/MWCNT networks cured with anhydride displayed an increase of the electrical conductivity of around three orders of magnitude with the addition of IL in a proportion of MWCNT/IL = 1:5 mass ratio. The effect of IL on dynamic mechanical properties and thermal conductivity was also evaluated. The improved thermal and electrical properties was attributed to the better dispersion of MWCNT within the epoxy matrix by IL, evidenced by transmission electron microscopy of the ER/MWCNT networks cured with anhydride. Raman spectroscopy was also used to confirm the interaction between MWCNT and IL. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43976.