Multifunctional hybrid organosilicate materials prepared by the sol-gel method

It has been shown that a comparison of the calculated parameters of solubility δ, activation energies of structure formation ΔG _str, and pH values of combined solutions makes it possible to predict and control the influence of the used chemical reagents on the aggregate stability of the composites and the properties of the synthesized gels. The synthesized gels possess high performance characteristics and can be used as sealing, compacting, and water isolation materials in construction, oil extraction, and other branches of industry.     

一种UV固化抗静电型硬化薄膜的制备

以六官能度聚氨酯丙烯酸酯预聚物和乙氧基化三羟甲基丙烷三丙烯酸酯单体为主体,甲基异丁基酮、丁酮和丙二醇甲醚为混合溶剂,1-羟基环己基苯基甲酮为光引发剂,纳米SiO_2分散液和导电高分子分散液CIL313为添加剂,有机硅聚醚为流平剂,制备了高硬度、耐摩擦抗静电型硬化薄膜,讨论了光引发剂用量、UV固化条件、纳米SiO_2分散液用量、流平剂、抗静电剂用量等对硬化薄膜外观与性能的影响。结果表明,当光引发剂用量8质量份,固化条件:200 mW/cm~2、300 mJ/cm~2,纳米SiO_2分散液用量30质量份,流平剂用量0.4质量份,抗静电剂用量10质量份时制备的硬化薄膜综合性能优异,其铅笔硬度3H5/5,耐摩擦性116次/200 g,表面电阻10~(10)Ω,全光透过率90.4%,雾度0.9%。     

Transparent UV curable antistatic hybrid coatings on polycarbonate prepared by the sol–gel method

UV curable, hard, and transparent organic–inorganic hybrid coatings with covalent links between the inorganic and the organic networks were prepared by the sol–gel method. These hybrid coating materials were synthesised using a commercially available, acrylate end-capped polyurethane oligomeric resin, hexanedioldiacrylate (HDDA) as a reactive solvent, 3-(trimethoxysilyl)propoxymethacrylate (MPTMS) as a coupling agent between the organic and inorganic phase, and a metal alkoxide, tetraethylorthosilicate (TEOS). The materials were applied onto polycarbonate sheets and UV cured, followed by a thermal treatment to give a transparent coating with a good adhesion and abrasion resistance. The high transmission and the thermogravimetric behaviour indicate the presence of a nanoscale hybrid composition. In a taber abrasion test, uncoated polycarbonate sheets exhibit a 48% decrease in light transmittance at 633 nm after 300 wear cycles, whereas the hybrid coating system containing 10 wt% silica shows only 10% decrease in light transmittance. For obtaining antistatic coatings, an intrinsically conductive polymer (ICP) was added to the optimised coating formulation. It is shown that the surface resistivity of the organic–inorganic hybrid coating can be reduced from 10¹⁶ to 10⁶ Ω for a high concentration of ICP in the coating formulation.     

用溶胶-凝胶法形成氧化铝硬质涂层的研究

讨论了溶胶-凝胶法制备铝胶的影响因素及A12O3的相变规律.探讨了A12O3涂层的涂层情况,总结出制备膜过程中消除发生团聚的方法,同时针对本实验提出了有效抑制团聚的方法.实验表明,用溶胶-凝胶法能够成功制备出均匀的A12O3涂层,当反应体系pH值为5,反应温度为30℃和溶液浓度为2.34mol·L-1时,加入3(wt)%PV溶液,采用自然干燥再经过1400℃高温煅烧能制得较为均匀连续的-A12O3涂层.     

Properties of PVC-titania hybrid materials prepared by the sol-gel process

Hybrid materials from Polyvinyl chloride (PVC) and titania were prepared using sol-gel technique. In-situ generation of titania network in the PVC matrix was carried out by introducing required amounts of tetrapropylorthotitanate (TPOT) followed by hydrolysis/condensation of TPOT in the matrix. Homogeneous and semi-transparent films were obtained by casting and solvent evaporation. Mechanical properties of these films up to 15 wt. % titania contents were studied. The results showed an increase in the Young's modulus, length at rupture and toughness of the unplasticised PVC. However, the tensile strength and stress at break point decreased with the addition of titania contents. Thermal stability of the material was studied using dehydrochlorination (DHCl) technique and thermogravimetric analysis. The PVC samples with small amount of titania were found to be more stable as compared with the pure PVC. Received: 13 October 1997/Revised version: 22 January 1998/Accepted: 2 February 1998     

溶胶-凝胶法制备SiO_2/水性聚氨酯杂化材料研究进展

主要介绍了有机-无机杂化材料的特点、溶胶-凝胶法的原理,并对溶胶-凝胶法制备二氧化硅(SiO_2)/水性聚氨酯(WPU)杂化材料的不同作用类型进行了综述。最后对SiO_2/WPU杂化材料存在的问题提出了解决措施及相关的建议,并对该杂化材料的发展方向进行了展望。     

UV curable EA-Si hybrid coatings prepared by combination of radical and cationic photopolymerization

A series of UV curable EA-Si hybrid coatings were prepared by a simple approach combining radical and cationic photopolymerization, with epoxy acrylate (EA) as monomer, γ-glycidoxypropyltrimethoxysilane (GPTMS) as inorganic precursor, benzophenone (BP) as free radical photo initiator and a diaryliodonium salt DPIHFP as cationic photo initiator. The chemical structures of EA-Si hybrid coatings were characterized by Fourier transform infrared (FTIR), Raman spectroscopy and X-ray diffraction (XRD). The thermal and optical properties of hybrid coatings were investigated by thermal gravimetric analysis (TGA) and UV–vis transmission spectroscopy, respectively. The results indicated that cross-linked network structure of SiOSi formed in the hybrid coatings, which led to the decrease in crystallinity and of EA-Si hybrid coating. The final conversion of CC bonds was also decreased because of the addition of GPTMS. The thermal stability of EA-Si hybrid coatings was enhanced in the second decomposition stage (300–400 °C) because of the existence of organic–inorganic cross-linked network structures. The transparency of coatings at around 346 nm tended to increase with increasing concentration of inorganic precursor GPTMS.     

溶胶-凝胶法制备γ-缩水甘油醚丙基三甲氧基硅烷/正硅酸乙酯杂化材料研究

采用溶胶-凝胶工艺制备γ-缩水甘油醚丙基三甲氧基硅烷/正硅酸乙酯(GPTMS/TEOS)杂化材料,采用正交实验法对H2O与S i的摩尔比、GPTMS与TEOS摩尔比、水解时间等影响材料性能的因素进行了优化,用热失重(TGA)和动电位扫描法研究分析了该材料的结构、耐热及防腐保护性能。结果表明:当GPTMS∶TEOS=1∶3(摩尔比),H2O∶S i=11.25∶1(摩尔比)时,该材料的耐热性及防腐保护性能最优,X射线衍射分析表明,该材料结构为非晶态结构。     

UV curable sulfonated hybrid materials and their performance as proton exchange membranes

In this study 2-acrylamido-2-methylpropanesulfonic acid (AMPS) containing UV curable nanocomposite membranes were prepared by using the sol–gel method. Tetraethylorthosilicate (TEOS), and 3-(methacryloyloxy)propyl trimethoxysilane (MAPTMS) were used, respectively as an inorganic precursor and coupling agent. Cross linking agents such as poly(ethylene glycol diacrylate) (PEGMA) and ethylene glycol dimethacrylate (EGDMA) were used to arrange the mechanical and physical properties of the resulting hybrid membrane. The hybrid formulation polymerized under UV irradiation and the gel percentage, water uptake of the membranes were calculated. The polymerization conversion of the organic part was investigated by using photo-differential scanning calorimetry (photo-DSC). The thermal and mechanical properties of the membranes indicated good stability. The morphological structure of membranes was investigated by scanning electron microscopy (SEM). In addition proton conductivity and methanol selectivity measurements were performed. The proton conductivity of the AMPS20–SOLGEL30 nanocomposite membrane is about 0.138 S cm^?1 at 50 °C. Selectivity toward methanol for the same membrane is very low with a selectivity factor of α = 0.032, which satisfies the requirements for DMFC applications.     

溶胶-凝胶法制备有机-无机杂化材料研究进展

综述了国内外溶胶-凝胶法制备有机-无机杂化材料的研究进展     

Study on acrylic resin/titania organic-inorganic hybrid materials prepared by the sol-gel process

Acrylic resin/titania organic-inorganic hybrid materials were prepared by the two approaches. One approach (BL method) was blending titania produced by the sol-gel process with synthesized acrylic resins containing various content of acrylic acid (AA). Another approach (IS method) was the in situ polymerization of acrylic monomers in synthesized titania sols. The structure and mechanical, thermal and optical properties of the hybrid films were investigated by small angle X-ray scattering (SAXS), atomic force microscopy (AFM), dynamic mechanical analysis (DMA), Instron testing machine, thermogravimetric analysis (TGA) and ultraviolet-visible spectroscopy (UV-VIS), respectively. Titania phase in the hybrids showed an open structure and nano-scale size. However, aggregation of titania occurred in the systems prepared by IS method or without AA contained. The mechanical properties, thermal stability and UV shielding properties of organic polymer were obviously improved with titania networks embedded. It was found that BL method could prepare homogeneous hybrids with better integrative mechanical properties in comparison with IS method.     

紫外光固化敷形涂布胶的制备与性能

用环氧丙烯酸树脂30-50份（质量,下同）,丙烯酸酯类单体40～65份,光引发剂2～5份,偶联剂及助剂0.1～3份,研制出可紫外光固化的敷形涂布胶,并测试了性能。结果表明,该胶具有较好的附着力,优异的耐湿热性和较快的表干速度,可满足印刷线路板的涂敷要求。     

Study of epoxidized-cardanol containing cationic UV curable materials

Cationic photopolymerization, thermal and mechanical properties of thin film materials containing bio-renewable cashew nutshell oil derivative – epoxidized-cardanol (ECD) were investigated. Higher and more consistent monomer conversion as a function of relative humidity was found for thin film materials containing 10 wt.% ECD and 5 wt.% hydroxy-functional reactive diluents during cationic photopolymerization. In addition, ECD imparted balanced physiochemical properties to the cationic UV curable materials. ECD showed great potential to be used as a reactive ingredient in cationic UV curable materials.     

UV curable acrylic dispersion for the cationic electro-deposition coating

Summary The vinyl group containing polymer was synthesized via radical polymerization of acrylic monomers followed by reaction with methacrylic oxyethyl isocyanate(MOI). Stable dispersions of the vinyl group containing polymer, pentaerythritol triacrylate(PETA) and photo initiator were prepared by neutralization of the above synthesized polymer with lactic acid. Electro-deposition process was introduced to apply UV-curable acrylic dispersion into the nickel-plated plastic substrate. The prepared dispersion containing PETA has higher particle size and higher deposition yield than those of the dispersion without PETA. The electro-deposited film was cross-linked by UV radiation after 10 minutes flash-off stage at 80 °C. The kinetic study by real-time FT-IR revealed that the cross-linked films containing PETA gave higher conversion than those without PETA resulting in harder film. Received: 29 June 2001 / Revised version: 2 October 2001 / Accepted: 4 October 2001     

全球辐射固化材料近期市场分析（一）

辐射固化技术于20世纪60～70年代,在欧美市场上初步确立了自身的产业地位,成为全球经济体系中的一个组成部分.各种专业分工不同的企业（原材料生产供应商、化学配方产品生产供应商、装置设备制造供应商和下游客户）,共同构建了UV/EB固化产业的价值链.近年来,世界三大主要地区（北美、欧洲和亚洲）辐射固化市场以近两位数的速度在增长,尽管全球经济形势持续低迷.2012年,全球辐射固化市场配方产品的消耗量据统计大约为457000t.亚洲市场消耗量已超过欧美市场而居全球首位.辐射固化配方产品在世界三大主要地区市场中应用的重点领域虽然各不相同,然而工业涂料在全球的市场份额中仍然比例最大.本文还列出了辐射固化原材料在不同市场中的消费量与价格.     

Characterization and properties of UV‐curable polyurethane‐acrylate/silica hybrid materials prepared by the sol‐gel process

UV‐curable, transparent hybrid material of urethane‐acrylate resin was prepared by the sol‐gel process using 3‐(trimethoxysilyl)propylmethacrylate (TMSPM) as a coupling agent between the organic and inorganic phases. The effects of the content of acid and silica on the morphology and mechanical properties of UV‐curable polyurethane‐acrylate/silica hybrid (UA‐TMSPM)/SiO₂ materials have been studied. The results of thermogravimetric analysis for the (UA‐TMSPM)/SiO₂ hybrid materials indicated that the thermal stability of the hybrids is greatly improved. It was found that with the increase of HCl content, the interfacial interaction between organic and inorganic phases had been strengthened, as demonstrated by field emission scanning electron microscopy. Without sacrificing flexibility, the hybrid materials showed improved hardness with increasing content of acid and silica. Compared with the pure organic counterpart UA/hexanediol diacrylate (UA/HDDA) system, abrasion resistance of the hybrids improved with increasing acid content, at low silica content. Copyright © 2004 Society of Chemical Industry     

Fabrication of UV curable coating for super hydrophobic cotton fabrics

A super hydrophobic cotton fabric was successfully prepared by a facile dip‐coating method using a synthetic fluorine‐free and UV curable super hydrophobic coating solution without additional particles. The obtained cotton fabric exhibited super hydrophobic property with a water contact angle above 159.5° and sliding angle 7.5°. Moreover, the treated cotton fabric could retain its super hydrophobic performance even after abrasion and accelerated laundering, as well as for different kinds of corrosive liquids. The coated cotton fabric was used to make up a surface tension‐driven, gravity‐assisted, floating oil–water separation device with separation efficiency above 99%. Additionally, the oil–water separation efficiency of super hydrophobic cotton fabric always was above 98% after 30 recycle times for cyclohexane–water mixture. POLYM. ENG. SCI., 59:E452–E459, 2019. © 2019 Society of Plastics Engineers     

Characterization of indium tin oxide (ITO) thin films prepared by a sol-gel spin coating process

Indium tin oxide (ITO) thin films were prepared by a sol-gel spin coating method, fired, and then annealed in the temperature range of 450-600°. The XRD patterns of the thin films indicated the main peak of the (2 2 2) plane and showed a higher degree of crystallinity with an increase in the annealing temperature. Upon annealing the films at 500 and 600°, two binding energy levels of Sn⁴⁺ ion of 486.9 eV and 486.6 eV, respectively, were measured in the XPS spectra. The ITO film that was annealed at 600° contained two oxidation states of Sn, Sn²⁺ and Sn⁴⁺, and it had a higher sheet resistance based on a rather low doping concentration of Sn⁴⁺. The film that was annealed at 500° and subsequently treated with 0.1 N HCl solution for 40 s showed a sheet resistance of 225 Ω/square. The surface treatment by the acidic solution diminished the RMS (root mean square) roughness value and the residual carbon content (XPS peak intensity of carbon) of the ITO films. It seems that the acid-cleaning of the ITO thin films led to a decrease of the surface roughness and sheet resistance.     

UV固化胶粘剂应用研究进展

论述了当前UV固化胶粘剂的应用现状,对UV固化胶粘剂配方中的主要原料预聚物、单体、光引发剂等的研究进展做了详细的阐述。     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.