Study on liquid oxygen compatibility of bromine‐containing epoxy resins for the application in liquid oxygen tank

The liquid oxygen compatible epoxy resin was obtained by the polycondensation between tetrabromobisphenol A and neat epoxy resins. The results of liquid oxygen impact test indicated that the synthetic epoxy resins were compatible with liquid oxygen. The relationship between impact reaction sensitivity (IRS) and flame retardancy were studied by liquid oxygen impact test and limiting oxygen index test. The results showed that the flame‐retardant modification of epoxy resin was valuable to reduce the IRS. The thermal gravimetric analysis results indicated that the Br · radical was quickly released in relatively low temperature (approximately 370°C) for compatible epoxy resin. The Br · radical was a key factor to promote the epoxy resin compatible with the liquid oxygen. The X‐ray photoelectron spectroscopy was used to survey the distribution of functional groups on the surface of samples before and after impact. The results showed that the oxidation reaction and carbonization process may occur on the surface of samples after impact. The liquid oxygen compatibility mechanism is proposed in this paper. The bromine‐containing epoxy resin has the potential to be the material used in liquid oxygen tank. Copyright © 2015 John Wiley & Sons, Ltd.     

用含螺环原碳酸酯的预聚物改性环氧树脂的研究

合成了一个新的螺环原碳酸酯单体，３，９ 二羟甲基 ３’，９’ 二苯基 １，５，７，１１ 四氧杂螺环［５，５］十一烷，它与二苯甲烷二异氰酸酯（ＭＤＩ）反应生成了低分子量预聚物，用该预聚物对环氧树脂进行改性，可以减少残留在树脂基体中的环氧基团，这说明该预聚物与环氧树脂之间发生了共聚固化反应．基体的Ｔｇ和热稳定性随预聚物加入量的增加而降低，但改性环氧树脂的粘接强度则随预聚物的加入量的增加而增加，螺环基团上的取代基对改性环氧树脂基体也有一定的影响，作者对上述试验观察到的现象进行了讨论．     

Evaluation of solubility parameters during polymerisation of amine‐cured epoxy resins

A new procedure for the calculation of solubility parameter evolution during polymerisation has been developed for amine‐cured epoxy systems, which allows quantitative thermodynamic modelling of chemically induced phase separation (CIPS). Solubility parameters calculation, chemical analysis based on near infrared spectroscopy and curing kinetics results obtained by differential scanning calorimetry will allow to model the evolution of the Flory–Huggins interaction parameter in amine‐cured epoxy blends. The resin system investigated was based on a diglycidyl ether bisphenol A (DGEBA) epoxy resin cured with isophorone diamine (IPD) blended with various reactive epoxydised dendritic hyperbranched polymer modifiers (HBP), yielding a CIPS‐controlled morphology. The analysis showed the evolution of the different contributions to the solubility parameters to follow the polymerisation kinetics. The dispersive contribution had the highest value at all stages of polymerisation, but the hydrogen and polar contributions showed the largest variation. By evaluating the dynamic evolution of the solubility parameter components, the Flory–Huggins interaction parameter in the epoxy resin‐hyperbranched polymer blends has been modelled as a function of time. This procedure, combined with thermodynamic modelling, will enable to predict phase diagrams in CIPS thermosetting blends quantitatively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1883–1892, 2000     

Effects of nanoclay on the thermal and rheological properties of a vartm (vacuum assisted resin transfer molding) epoxy resin

Three types of commercially available organophilic Montmorillonite (Cloisite 30B, 25A and 15A) were used to prepare VARTM epoxy resin nanocomposites in order to study the effect of the nanoclay organophilic modification on the epoxy matrix. The morphology of the dispersions was investigated through XRD and TEM analyses. The thermal stability of the nanocomposites was studied by means of HI-RES TG measurements and the influence of the nanoclay on the viscosity of the resin was investigated through rheological measurements. It was found that the nanoclay modification had no significant influence on the dispersion and on the thermal properties of the nanocomposites. Areas of exfoliated and intercalated morphology were observed. The viscosity of the resin furthermore did not exceed the critical value of the infusion process.     

Plasma treatments of PET meshes for fuel-water separation applications

Sulphur hexafluoride (SF(6)) plasma treatments and hexamethyl disiloxane (HMDSO) plasma polymerisation were performed on poly(ethylene terephthalate) (PET) meshes and the resulting wettability against liquids having very different surface tensions were investigated at the light of a possible use of the materials in the fuel/water separation technology. Surface modification of the meshes owing to HMDSO plasma polymerisation followed by SF(6) plasma treatment was also investigated. Hydrophobic performances were characterised refining the conventional Wilhelmy dynamic contact angle (DCA) technique, using several reference solutions having the surface tension values between 20-72 mN/m. Measurements of the water intrusion pressure (WIP) of the treated samples were also performed. Surface modifications on the plasma treated meshes were investigated by means of Fourier-transform infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis. SF(6) and HMDSO plasma treatments decrease the surface energy of the PET meshes, lowering the liquid surface tension at which the wettable/unwettable transition occurs and increasing the WIP. Moreover, an increase in hydrophobic performances was achieved with HMDSO plasma polymerisation followed by SF(6) plasma treatment.     

PREPARATION AND PROPERTIES OF EPOXY RESIN MODIFIED BY LIQUID CHLOROPRENE-HYDROXYETHYLMETHACRYLATE COPOLYMER

The epoxy resin modified by liquid chloroprene-hydroxyethylmethacrylate copolymer (CP-HEMA) is a new kind of structural adhesives with good mechanical properties. By changing its mole-cular structure, it may also have such desirable properties as retardation of combustion, enduringweather aging, inert oils and chemicals. A series of the thermosets of the epoxy resin modifiedby CP-HEMA used as a toughener were prepared. The effects of CP-HEMA content, catalyst con-tent and curing temperature on the mechanical properties of modified epoxy resin system were studied.The thermal weight-loss curves were examined. The two-phase morphology was observed and dis-cussed.     

一种液晶环氧增韧环氧树脂的研究

环氧树脂具有优异的机械性能 ,耐高温以及良好的加工工艺性 .被广泛用于机械、航天、船舶等领域 .由于环氧树脂固化后断裂延伸率小 ,脆性大 ,使其应用受到了一定的限制 .为此 ,国内外学者对环氧树脂进行了大量的改性研究工作 .用含有“柔性链段”的固化剂固化环氧 ,在交联网络中引入柔性链段[1] ;在环氧基体中加入橡胶弹性体[2 ] 、热塑性树脂[3 ,4] 、液晶聚合物[5,6] 等分散相或用热固性树脂连续贯穿于环氧树脂网络中形成互穿、半互穿网络结构[7] ,以改善环氧树脂的韧性 .本文采用液晶环氧化合物原位复合增韧环氧树脂 ,考察了液晶环氧对环…     

Synthesis and characterization of liquid crystalline epoxy and co-polymerisation with a non-mesomorphic epoxy resin

A novel liquid crystalline epoxy resin based on the imine group was synthesised and structurally characterised by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. The mesogenic behaviour of the monomer was measured by differential scanning calorimetry (DSC) and polarised optical microscopy (POM), and presented various textures in the extensive temperature range. Methyl nadic anhydride (MNA) was employed to cure the liquid crystalline epoxy resin and the curing process was investigated using POM and wide-angle X-ray diffraction (WAXD). Information about distribution of liquid crystalline epoxy resin in the blending system resulted from the FT-IR Imaging System, indicating that molecules of liquid crystalline epoxy resin can agglomerate to form anisotropic domains. The improvement in mechanical properties of diglycidyl ether of biphenol A (DGEBA) modified with liquid crystalline epoxy was achieved. Scanning electronic microscopy (SEM) showed that an extremely rough and highly deformed fracture surface can be obtained. DGEBA modified with liquid crystalline epoxy resin was characterised by dynamic mechanical analysis (DMA) for its thermal properties. The results indicate that the presence of the liquid crystal phase influences glass transition temperature (Tg).     

Network morphology and electro-optical characterisations of epoxy-based polymer stabilised liquid crystals

ABSTRACT

In this paper, by utilising the photoinitiated cationic polymerisation of liquid crystalline epoxide in LC solvents, the epoxy-based polymer stabilised liquid crystals (EPSLCs) were fabricated. The effects of the liquid crystalline epoxide content, UV intensity, polymerisation temperature, and initiator content on the network morphology of liquid crystalline epoxy polymers (LCEPs) and electro-optical characterisations of EPSLC samples were studied. The results suggested that the preparation conditions had a dominant effect on the morphology of the LCEP and the void size in the EPSLC sample. The increase of liquid crystalline epoxide content, UV intensity, and initiator content induced that the density of LCEP network became larger and the void size decreased, which resulted in that the stabilising effect from the LCEP network on the mesogenic solvent molecules was strengthened. Conversely, the increase of polymerisation temperature induced that the stabilising effect from the LCEP network on the LC molecules was weakened.     

自乳化水性环氧树脂乳液的研制

利用化学改性的方法制备自乳化型水性环氧树脂乳液。采用二乙醇胺部分开环环氧树脂,并采用聚醚多胺进行扩链,制备可自分散的阳离子水性环氧树脂乳液。本文研究了乳液研制时共溶剂丙二醇甲醚、环氧树脂分子量、二乙醇胺用量、不同的聚醚多胺、聚醚多胺D-230用量、HAC用量对乳液稳定性的影响。并对乳液性能进行测试,结果表明,该乳液具有良好的贮存稳定性,VOC含量低,涂膜综合性能优良等特点,该乳液为环保型产品。     

Re-examination of the Reactivity of N-Carboxy Amino Acid Anhydrides 1. Polymerisation of Amino Acid NCAs in Acetonitrile and in the Solid State in Hexane

Ring-opening polymerisation of N-carboxy anhydrides of γ-benzyl-L- glutamate, L-alanine and L-leucine by a primary amine initiator in acetonitrile and in hexane was examined, with care taken to avoid contamination by moisture. The polymerisation of amino acid NCAs initiated by butylamine in hexane proceeded in the crystalline state (solid state) because the NCA crystals did not dissolve in hexane. Although amino acid NCAs were believed to polymerise completely in acetonitrile, polymerisation of the amino acid NCAs in acetonitrile was found to stop at around 20% conversion. As resulting polypeptides did not dissolve in acetonitrile, the polymer terminals were considered to be occluded in the polymer precipitate. On the other hand, each amino acid NCA was much more reactive in the solid state in hexane than in acetonitrile. Especially, L-leucine NCA showed remarkable reactivity in the solid state. The reactivity in the solid state was explained with reference to the crystal structure.     

Dynamic mechanical properties of epoxy/novolac system modified with reactive liquid rubber and carbon filler

This paper reports on the work carried out to evaluate the frequency dependent viscoelastic properties of epoxy/novolac compositons modified with a liquid reactive rubber and carbon filler. For epoxy systems modified with elastomer, three typical transitions were observed: the α-relaxation deeply related to the glass transition of epoxy, the β-transition of epoxy, and the glass transition of rubber appeared near to the β-relaxation of epoxy resin. Considering an Arrhenius equation, the activation energies of β-relaxation were estimated. In the region of glass transition and rubbery state the temperature dependence of the shift factor (α_T) was determined through Williams-Landel-Ferry (WLF) equation.     

环氧树脂增韧改性的研究进展

概述了近年来互穿聚合物网络（IPN）、刚性粒子增韧环氧树脂的研究现状,并展望了环氧树脂增韧改性研究的前景。     

Preparation of highly exfoliated epoxy/clay nanocomposites by clay grafted with liquid crystalline epoxy

Epoxy/clay nanocomposites with a high degree of exfoliation were achieved by intercalating liquid crystalline epoxy into clay intragallery as well as using a so-called ‘solution compounding’ process. In this process, clay modified was first treated with trichloromethane to form organoclay-trichloromethane suspension followed by liquid crystalline epoxy modification. The liquid crystalline epoxy grafted clay was then mixed extensively with epoxy to form epoxy/nanoclay composites. The mechanism of exfoliation was explored by monitoring the change of morphology of organoclay during each stage of processing with X-ray diffraction (XRD). The liquid crystalline epoxy grafted clay synthesised was characterised by fourier transform infrared spectroscopy (FT-IR) and polarising optical microscopy (POM). The clay platelets uniformly dispersed and highly exfoliated in the whole epoxy matrix were observed using transmission electron microscopy (TEM) and FT-IR imaging system. The epoxy nanocomposites were fabricated by incorporating different liquid crystalline epoxy grafted clay loading. The results revealed that the incorporation of liquid crystalline epoxy grafted clay resulted in a significant improvement in glass transition temperature (Tg) derived from dynamic mechanical analysis (DMA) and thermal stability measured by thermogravimetric analysis (TGA).     

Preparation and Properties of Pyrene-Modified Multi- Walled Carbon Nanotube/Epoxy Resin Nanocomposites

Nanocomposites of multi-walled carbon nanotube (MWCNT)/bis-phenol A type epoxy resin were prepared and physical properties of the nanocomposites were investigated. For the fine dispersion of MWCNT in the epoxy resin, MWCNT was modified with pyrene butyric acid (PBA) in the supercritical carbon dioxide (CO₂). The physical adsorption of PBA on the surface of MWCNTs was studied with a thermogravimetric analyzer and a transmission electron microscopy. The electrical surface resistivities of the nanocomposites showed threshold decreases due to percolations above the critical concentration of the MWCNT. The resistivities showed maximum depending on the concentration and the modification of the surface of the MWCNT with PBA. It is postulated that the dispersion of the MWCNT in epoxy resins resulted in dispersion systems which exhibit rheological properties similar to lyotropic liquid crystalline polymers. The surface resistivities of the MWCNT/epoxy systems reflected the morphological characteristics of the systems which also determined rheological properties of the systems.     

Effects of organo-montmorillonite dispersion on thermal stability of epoxy resin nanocomposites

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo-montmorillonite (O-MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The dispersion state of the MMT in the matrix was investigated by X-ray diffraction and scanning electronic microscopy. The thermal stability of the epoxy nanocomposites was examined by TGA. Thermal stability of the epoxy nanocomposite is dependent upon the dispersion state of the OMMT in the epoxy matrix although all the epoxy nanocomposites had enhanced thermal stability compared with the neat epoxy resin. The thermal stability of the epoxy resin nanocomposites was correlated with the dispersion state of the MMT in the epoxy resin matrix.     

环氧树脂微流控芯片的表面功能化修饰

利用微流控芯片进行生物医学检测,往往需要对芯片通道进行表面修饰,连接上某些特异性的活性分子。本研究对一种新型的环氧树脂材料表面进行空气等离子体前处理,然后进行丙烯酸(acrylic acid, AAc)紫外诱导接枝聚合,使这种环氧树脂材料表面引入了羧基基团.在此基础上,将这种化学惰性的环氧树脂表面连接上特异的抗体,作为微流控芯片的基底,进行免疫检测实验。用静态接触角、甲苯胺兰染色、X射线光电子能谱分析（XPS）、BCA蛋白定量检测和细胞黏附实验等检测手段对环氧树脂的表面修饰进行了表征。结果表明,使用空气等离子体处理后丙烯酸紫外诱导接枝聚合的方法成功地在环氧树脂表面引入了大量的羧基基团;使用EDC/NHS偶联试剂,将蛋白以共价连接的方式连接到疏水的、化学惰性的环氧树脂表面;通过细胞黏附实验表明,用这种方法修饰的环氧树脂表面可以用作生物医学的免疫检测实验。     

银包玻珠核壳复合粒子的表面处理及环氧导电胶的电性能

以化学还原法合成的银包玻珠核壳复合粒子(Ag/GM)为原料, 乙二胺为表面处理剂, 制备了表面吸附有乙二胺的Ag/GM, 并用它作为导电填料组成了导电胶. 与化学还原法直接合成或沸水处理的Ag/GM相比, 乙二胺处理的Ag/GM能更有效地分散在环氧树脂胶黏剂中, 且能与环氧树脂基体产生化学键合, 降低Ag/GM和环氧树脂基体间的界面能, 用其制备的导电胶的导电率较高, 导电渗滤阈值较低. 同时, 结合导电网络理论和等效电路图, 阐明了用乙二胺处理的Ag/GM作填料制备的导电胶具有较低体积电阻率的原因.     

Surface modified multi-walled carbon nanotubes in CNT/epoxy-composites

Multi-walled carbon nanotubes (MWCNTs), produced by arc-discharge method, were treated with oxidising inorganic acids. The surface modification of the oxidised nanotubes (o-MWCNTs) was achieved by refluxing the tubes with multi-functional amines. The functionalised nanotubes were embedded in the epoxy resin and the resulting composite was investigated by transmission-electron microscopy (TEM). The functionalisation led to a reduced agglomeration and evidences are given for improved interaction between the nanotubes and the epoxy resin.     

液体氯丁二烯-甲基丙烯酸羟乙酯共聚物改性环氧树脂——N,N-二甲基苄胺固化体系

本工作制备了一系列以N,N-二甲基苄胺为固化剂的液体氯丁二烯-甲基丙烯酸羟乙酯共聚物改性环氧树脂固化物。研究了液体共聚物用量和固化条件对改性体系物理性能的影响。用红外光谱法和固化仪方法,测定了固化反应速度,讨论了固化反应机理。用扫描电镜的方法,观察了液体共聚物用量和固化条件对改性体系形态结构的影响。