环氧树脂／蒙脱土纳米复合材料的制备与性能

重点综述了影响蒙脱土片层在环氧基体中剥离的主要因素。根据环氧树脂／蒙脱土纳米复合材料的结构特点,解释了其力学性能、热性能、耐腐蚀和阻隔性能得到明显改善的原因。     

环氧树脂/有机化蒙脱土纳米复合材料的研究

采用插层原位聚合法制备了环氧树脂/有机化蒙脱土(EP/OMMT)纳米复合材料,探讨了OMMT的剥离结构及其对EP/OMMT纳米复合材料热性能和力学性能等影响。结果表明:当w(OMMT)=7%时,EP/OMMT纳米复合材料的热变形温度提高了24～27℃,Tg(玻璃化转变温度)提高了20～30℃,并且其力学性能和耐湿热性能均优于纯EP体系。     

负载羧基有机蒙脱土制备环氧树脂纳米复合材料

用椰油酰胺丙基甜菜碱(CAB)制备了1种负载羧基的有机蒙脱土,并将这种有机蒙脱土加入甲基四氢苯酐固化环氧树脂体系中制得环氧树脂/蒙脱土纳米复合材料。采用XRD衍射和透射电镜TEM研究了蒙脱土有机化前后和在纳米复合材料中的片层结构和形态。用TGA研究了纳米复合材料的热稳定性能。结果表明,制备的负载羧基蒙脱土充分插层且很容易分散在环氧树脂中得到纳米复合材料。其热稳定性和有机蒙脱土在树脂中的分散状态有关。     

Morphology and mechanical properties of UV-curable castor oil-based waterborne polyurethane/organic montmorillonite nanocomposites

Water resistance is a unique advantage of castor oil-based polyurethane, permitting the application of coatings in humid environments. However, its low thermal decomposition temperature remains a limitation. Here, to demonstrate a simple method to improve the thermal stability of cured films, we prepared an organic montmorillonite dispersion utilising 3-(methacryloyloxy)propyltrimethoxysilane and protonated 3-aminopropyltriethoxysilane for modifying the clay. The method was put into practice by directly mixing the dispersion with a UV-curable castor oil-based waterborne polyurethane dispersion. The inclusion of organic molecule chains from the silane coupling agents noticeably improves the compatibility of polyurethane with organic montmorillonite, which imparts the composite latex with better thermal stability and mechanical properties when the organic montmorillonite additive is 5.0?wt-%.     

水性环氧树脂包覆有机蒙脱土制备木材胶粘剂

摘要：水性环氧树脂通常含有水溶性分子或分子链，导致在高温和潮湿条件下作为木材胶粘剂时耐水性及力学性能较差。采用有机改性的纳米蒙脱土改性水性环氧树脂增强水性环氧树脂胶粘剂的耐水性及力学性能。并通过乳液包覆蒙脱土的方法与直接共混的方法对比，研究了不同添加量有机蒙脱土（0%，3%，6%，9%）对胶粘剂性能的影响。胶粘剂的耐水性及力学性能通过测量胶粘剂在干燥及潮湿条件下的剪切强度来表示。通过TGA、SEM、TEM、DSC研究了复合胶粘剂的热稳定性和结构。结果表明，在水性环氧树脂中添加有机改性的纳米蒙脱土，可以有效地提高胶粘剂的粘结强度，此外，采用乳液包有机覆蒙脱土的方法比直接共混的方法制备得到胶粘剂，有机蒙脱土在胶粘剂中分布更均匀，具有更优异的力学性能，说明有机蒙脱土在复合材料中的分散质量是影响复合胶粘剂性能的主要原因。     

环氧树脂增容的聚氯乙烯/蒙脱土纳米复合材料的光学性能

环氧树脂具有辅助聚氯乙烯(PVC)插层有机蒙脱土(OMMT)层片的作用.环氧树脂的加入对复合材料的光学透明性有不利的影响,但是随着OMMT用量的增大,材料的光学透明性显著提高;同时环氧树脂还改善了复合材料的加工热稳定性.     

有机蒙脱土改性环氧树脂胶粘剂的制备工艺优化设计

采用不同碳链的季铵盐阳离子作为插层剂与蒙脱土层间的无机阳离子(Ca2+)交换,制备出系列有机蒙脱土,用有机蒙脱土对环氧树脂进行改性,制备了纳米有机蒙脱土/环氧树脂结构胶,同时,用4因素3水平正交试验设计对关键配料参数进行了优化,并对结构胶的剪切强度和冲击强度进行了测试。研究表明,优化配制的纳米改性环氧树脂胶粘剂是一种高性能的结构胶粘剂,其钢-钢剪切强度可达29.2 MPa,冲击强度可达33.8 MPa,有效地改善了环氧树脂胶粘剂的粘接性能。     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Mechanical and damping properties of epoxy/liquid rubber intercalating organic montmorillonite integration nanocomposites

Two different kinds of micro‐nanoconstrained damping structure units (M‐NCDSUs) were prepared by carboxyl‐terminated butadiene acrylonitrile copolymer and epoxy‐terminated butadiene acrylonitrile copolymer liquid rubbers intercalating organic montmorillonite, respectively. The prepared M‐NCDSUs were then blended with epoxy resin to obtain damping structure integration nanocomposites. The X‐ray diffraction and transmission electron microscope measurements applied for the obtained samples confirmed the good formation of M‐NCDSUs in the epoxy network. The tensile strength decreased slightly with the addition of M‐NCDSUs, whereas the damping properties measured by dynamic mechanical analysis showed a remarkable increase. Besides, the cured epoxy resin exhibited a two‐phase morphology where the spherical rubber phase dispersed uniformly in the epoxy matrix. The nanocomposites containing M‐NCDSUs showed superior comprehensive properties compared with that without the functional units. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39797.     

醇酸树脂微胶囊的制备及环氧涂层自修复性能

采用三聚氰胺-脲醛树脂（MUF）为壁材、合成的花椒籽油醇酸树脂为芯材,原位聚合法制备自修复微胶囊,探讨了微胶囊的制备工艺。并采用扫描电子显微镜（SEM）、红外光谱仪（FTIR）、热重分析仪（TGA）和粒径分析仪对微胶囊的表面形貌、化学结构、热稳定性及其粒径分布进行了测试表征。将醇酸树脂微胶囊分散到环氧基体中,研究了环氧涂层的力学性能和自修复性能。实验结果表明,当乳化剂浓度为2.0g/L、芯壁比为2∶1、终点pH为3.5时,微胶囊呈球形结构,无明显的缺陷和损伤,平均粒径为97.44μm,热稳定性良好。当添加质量分数5%的微胶囊时,与未添加微胶囊的自修复涂层相比,其弯曲强度、拉伸强度、黏结强度及其冲击强度分别提高了50.4%、50.0%、40.0%及25.2%,且涂层的自修复性能良好。     

环氧树脂/环氧液晶/蒙脱土纳米复合材料研究

采用液晶环氧预聚物(PHQEP)与有机蒙脱土(OMMT)共混改性环氧树脂制备三元共混体系的环氧基复合材料。用X射线衍射法(XRD)测试了有机化蒙脱土在被插层前后片层间距的变化,通过DSC、TGA及SEM等对PHQEP/OMMT增韧改性环氧树脂固化体系的力学性能,热性能及微观相态结构进行了研究。结果表明:当PHQEP质量分数为5%,添加1.5%的有机蒙脱土可以使环氧树脂的冲击强度达到最大值23.43 kJ/m2,比纯环氧树脂提高2倍左右,玻璃化转变温度及5%热分解温度比纯环氧树脂分别高出15℃和27℃。PHQEP与OMMT的加入使纳米复合材料的力学性能和热性能得到明显提高。     

三聚氰胺-甲醛树脂／蒙脱土纳米复合材料的研制

采用微波加热离子交换树脂交换法将天然钙蒙脱土转变为镍基蒙脱土。三聚氰胺单体与镍基蒙脱土层间镍离子的络合后,加入甲醛经插层原位聚合制备三聚氰胺-甲醛树脂/蒙脱土纳米复合材料。X射线粉末衍射结果显示,三聚氰胺-甲醛树脂/蒙脱土复合物试样的d_(001)值由1．41nm增至1．84nm,说明蒙脱土的硅酸盐片层被撑开。粘接剪切强度测试结果表明,蒙脱土的加入提高材料的粘接性能。     

Multifunctional Cu2+‐montmorillonite/epoxy resin nanocomposites with antibacterial activity

Multifunctional nanocomposites can be achieved by addition of modified layered nanoclays to impart to the final materials a designed set of properties. The easy reproducible preparation of copper modified montmorillonite has been reported here together with its spectroscopic characterization, including ²⁹Si NMR in the solid state. Epoxy‐nanocomposites and glass fiber reinforced laminates containing 1% wt and 3% wt of Cu²⁺‐MMT have been prepared and characterized. Thermal and mechanical properties have been evaluated. The experiments carried out to evaluate the antibacterial activity showed that the epoxy‐resin nanocomposites with 3% wt of Cu²⁺‐MMT exhibited an inhibition action higher than 96% against Escherichia coli and Staphylococcus aureus. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44733.     

Cure behavior of epoxy resin containing castor oil and cashew nut shell liquid and its derivative

The cure behavior of epoxy resin with a conventional amide‐type hardener (HD) was investigated in the presence of castor oil (CO), cashew nut shell liquid (CNSL), and cashew nut shell liquid–formaldehyde resin (CFR) with dynamic differential scanning calorimetry (DSC). The activation energy of the curing reaction was also calculated on the basis of nonisothermal DSC thermograms at various heating rates. A one‐stage curing was noted in the case of epoxy resin filled with CO, whereas the epoxy resin with CNSL and CFR showed a two‐stage curing process. A competitive cure reaction was noted for the epoxy resin/CNSL(or CFR)/HD blends. In the absence of HD, CFR showed lower values of curing enthalpy than that of CNSL. The activation energy of epoxy resin curing increased with increasing CNSL and CFR loading. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

剥离型酚醛树脂/蒙脱土纳米复合材料研究

用十六烷基三甲基溴化铵(CTAB)对蒙脱土进行了有机化处理,使蒙脱土由亲水性变成亲油性。采用XRD、FTIR及TEM研究了有机蒙脱土及其在酚醛树脂中的剥离行为,制备了酚醛树脂/蒙脱土纳米复合材料并测试了其层间剪切性能和烧蚀性能。实验结果表明,经CTAB处理的蒙脱土与酚醛树脂具有良好的相容性,且CTAB的含量较多时所制得的有机蒙脱土的结构较好,根据Bragg方程计算,CTAB用量超过蒙脱土量50%时,蒙脱土的片层间距由原来的1.48 nm增加到2.33 nm;有机蒙脱土用量小于5%时生成完全剥离型酚醛树脂/蒙脱土纳米复合材料;与碳布增强酚醛树脂复合材料相比,碳布增强酚醛树脂/蒙脱土纳米复合材料的力学性能和烧蚀性能均有一定的提高和改善,层间剪切强度随蒙脱土含量的增多而增大,蒙脱土用量为15%时,层间剪切强度提高了27.1%,线烧蚀率在用量为3%时降低了48.5%,质量烧蚀率变化不明显。     

纳米有机蒙脱石改性环氧树脂的研究

利用长链的有机阳离子改性天然蒙脱石，制备出有机蒙脱石，用于改性环氧树脂。在有机蒙脱石低含量范围，环氧树脂有机蒙脱石复合物的触变性得到了显著改善；同时将固化产物的热降解温度从380．4℃提高至397．4℃。     

Intercalation of epoxy resin in organically modified montmorillonite

Various methods of preparation of epoxy resin/clay mixtures, before the addition of the crosslinking agent and curing to form epoxy‐based polymer layered silicate (PLS) nanocomposites, have been investigated to determine their effect on the nanostructure. Organically modified montmorillonite clay was used, and the mixtures were prepared by both simple mixing and solvent‐based methods. X‐ray diffraction shows that intercalation of the resin into the clay galleries occurs for all clay loadings up to 25 wt % and for both preparation methods, but the dispersion of the clay in the resin, observed by optical microscopy, is significantly better for the solvent preparation method. Differential scanning calorimetry (DSC) shows that the intercalated resin has the same molecular mobility as the extra‐gallery resin, but suggests that the intercalated resin does not penetrate completely into the galleries. Prolonged storage of the resin/clay mixtures at room temperature leads to changes in the DSC response, as well as in the response to thermogravimetry, which are interpreted as resulting from homopolymerization of the epoxy resin, catalyzed by the onium ion in the modified clay. This confirms and explains the earlier observation of Benson Tolle and Anderson (J Appl Polym Sci 2004, 91, 89) that “conditioning” of the resin/clay mixtures at ambient temperature has a significant effect when the crosslinking agent is subsequently added, and indicates that the preparation method has important consequences for the nanostructure development in the PLS nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3751–3763, 2006     

环氧树脂/蒙脱土纳米复合材料的制备和性能

利用插层法制备了环氧树脂/蒙脱土纳米复合材料。X射线衍射分析表明,改性使蒙脱土层间距变大,制备出的环氧树脂/蒙脱土纳米复合材料剥离结构较好。性能测试表明,复合材料的力学性能和热性能均比纯环氧树脂有所提高:拉伸强度提高了70.8%,无缺口冲击强度提高了64.5%,热变形温度提高了17.7℃。     

Impact modified epoxy/montmorillonite nanocomposites: synthesis and characterization

Diglycidyl ether of bisphenol A type epoxy resin-polyether polyol-organically treated montmorillonite ternary nanocomposites were synthesized in this study. The effects of addition of polyether polyol as an impact modifier on morphological, thermal and mechanical properties of nanocomposites were investigated by X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry, impact and tensile testing. The results showed that organically treated montmorillonite is intercalated by epoxy, since the interlayer spacing expanded from 1.83 to 3.82 nm upon nanocomposite synthesis. The addition of polyether polyol impact modifier had no effect on the interlayer spacing. SEM examination showed that polyol forms an immiscible phase in the epoxy matrix. Thermal characterization of nanocomposites indicated an increase in T_g with respect to both polyether polyol and montmorillonite contents. The impact strength of the samples with no clay was improved approximately 160% upon adding 7 wt% polyether polyol. In polyether polyol modified nanocomposites, the impact and tensile strengths decreased with respect to increasing amount of montmorillonite and showed a maximum with respect to the polyether polyol content at constant clay loading. The Young's modulus of the nanocomposites exhibited an increase with respect to the montmorillonite loading and showed a maximum with respect to the polyol content at each clay loading.     

环氧树脂改性聚乳酸/低熔点尼龙6/蒙脱土纳米复合材料结构与性能

通过熔融共混法制备了环氧树脂改性聚乳酸 (ePLA)/低熔点尼龙6 (LMPA6)/蒙脱土纳米复合材料。XRD和DSC结果表明,结晶度随着有机蒙脱土（OMMT）加入量的增加呈先增加后减小的趋势。流变行为结果表明,ePLA/LMPA6/OMMT纳米复合材料的黏性响应占主导地位,另外,随着OMMT加入量的增加,储能模量和损耗模量也增加。阻隔性能测试结果表明,OMMT的加入能够有效地改善纳米复合材料的阻隔性能。热重结果表明,OMMT的加入能够显著提高纳米复合材料的热稳定性能。TEM测试结果表明,OMMT加入量较少时,OMMT容易在基体中形成均一的纳米结构。力学性能分析表明,随着OMMT质量分数的增加,纳米复合材料的拉伸强度、断裂伸长率和冲击强度均出现先上升后下降的趋势,且当OMMT质量分数为3%时,纳米复合材料的力学性能均达到最大值,与未加OMMT时相比,分别提高了9.7%、37.8%和35.9%。