技术领域technical field
本发明涉及一种降低丙烯酸酯材料表面能的方法。该方法是通过合适的工艺条件合成一种含氟丙烯酸酯和制备粒径均匀、分散稳定的球型纳米二氧化硅有机溶胶，在丙烯酸酯材料制备过程中加入上述的含氟丙烯酸酯和有机二氧化硅溶胶，也就是以含氟丙烯酸酯和纳米二氧化硅与丙烯酸酯单体共聚杂化，形成杂化材料以降低丙烯酸酯材料表面能。The invention relates to a method for reducing the surface energy of acrylate materials. The method is to synthesize a fluorine-containing acrylate and prepare a spherical nano-silica organosol with uniform particle size and stable dispersion through proper process conditions, and add the above-mentioned fluorine-containing acrylate and organic Silica sol, that is, fluorine-containing acrylate and nano-silica and acrylate monomers are copolymerized and hybridized to form hybrid materials to reduce the surface energy of acrylate materials.
丙烯酸酯材料已在涂料领域得到广泛应用。丙烯酸酯树脂涂料有很强的光、热和化学稳定性，理想的力学性能和配方的可设计性，使其广泛用于飞机、汽车、仪器设备、建筑、家用电器、道路桥梁、纺织、食品器皿等领域。在丙烯酸酯树脂中引入含氟基团可改变丙烯酸酯聚合物的性能，改性后的丙烯酸酯聚合物不但保持了漆膜原有的特性，而且有效地提高了漆膜的耐久性、抗污性，应用更加广泛。Acrylate materials have been widely used in the field of coatings. Acrylic resin coatings have strong light, heat and chemical stability, ideal mechanical properties and designability of formulations, making them widely used in aircraft, automobiles, instruments and equipment, construction, household appliances, road bridges, textiles, food Utensils and other fields. The introduction of fluorine-containing groups into the acrylate resin can change the performance of the acrylate polymer. The modified acrylate polymer not only maintains the original characteristics of the paint film, but also effectively improves the durability and anti-fouling of the paint film. properties, the application is more extensive.
纳米材料可改善和提高聚合物材料的性能，所形成的有机高分子-无机纳米杂化材料可显著提高材料的硬度、耐磨性和耐刮擦性，还可以具备新的性能。近年来，对于用含氟丙烯酸酯，或用纳米材料来改善丙烯酸酯类漆膜性能的研究已有报道。合成新的含氟丙烯酸酯单体并结合采用新的纳米材料工艺与丙烯酸酯聚合物基体相互作用产生新的效应，实现二者之间优势的互补，可有效降低丙烯酸酯材料的表面能，开发性能优异的新的丙烯酸酯材料。Nanomaterials can improve and enhance the performance of polymer materials, and the formed organic polymer-inorganic nano-hybrid materials can significantly improve the hardness, wear resistance and scratch resistance of materials, and can also have new properties. In recent years, there have been reports on the use of fluorine-containing acrylates or nanomaterials to improve the properties of acrylate paint films. Synthesis of new fluorine-containing acrylate monomers combined with the use of new nano-material technology to interact with the acrylate polymer matrix to produce new effects, to achieve complementary advantages between the two, can effectively reduce the surface energy of acrylate materials, and develop New acrylate material with excellent performance.
背景技术Background technique
氟原子由于具有很强的电负性，取代有机物碳氢键上的氢原子后，可以赋予物质很高的表面活性。含全氟烷基基团的氟聚合物具有低的表面自由能，赋予材料表面拒水拒油、抗污防粘性能。Zisman在1962年已报道(甲基)丙烯酸全氟烷基酯均聚物中侧链全氟代亚甲基单元超过7个时就具有极低的表面能(10～11mN/m)(J Phys Chem，1962，66：1207-1208)。含氟丙烯酸酯由于具有良好的成膜性和粘附作用，与其它丙烯酸酯共聚可以得到性能优异的含氟聚合物。含有氟支链的丙烯酸酯共聚物具有超低表面张力和高氧渗透性，水吸收低、耐化学性高。聚合物材料百科全书(Polymeric materials encyclopedia，Boca Raton：CRC Press.1996.1536)中介绍了含氟涂料给予织物、纸张、皮革表面拒水拒油性和抗污性。含氟丙烯酸酯单体主要有两条合成路线：(1)由氟化醇与(甲基)丙烯酸酯化合成；(2)由全氟碘烷与(甲基)丙烯酸盐反应而得，主要有3M、Du Pont、Hoechst、旭硝子、大金工业和大阪有机化学等公司生产。研究论文(高分子学报，2002，6：770-774)报道了全氟辛酸与甲基丙烯酸羟丙酯反应合成甲基丙烯酸全氟辛酰氧丙基酯，该含氟丙烯酸酯均聚物的表面能为14.2mN/m。目前国内外对含氟丙烯酸酯单体的研究(Macromolecules，1997，30：2883-2890；Macromolecules，2002，35：1658-1662；高分子学报，2004，(2)：196-200)主要集中为(甲基)丙烯酸全氟烷基(C6～C9)乙酯。Due to the strong electronegativity of the fluorine atom, after replacing the hydrogen atom on the carbon-hydrogen bond of the organic substance, it can endow the substance with a high surface activity. Fluoropolymers containing perfluoroalkyl groups have low surface free energy, which endows the surface of the material with water and oil repellency, anti-fouling and anti-sticking properties. Zisman had reported in 1962 that (meth) acrylate perfluoroalkyl ester homopolymer had extremely low surface energy (10-11mN/m) when the side chain perfluoromethylene units exceeded 7 (J Phys Chem, 1962, 66:1207-1208). Since fluorine-containing acrylate has good film-forming properties and adhesion, it can be copolymerized with other acrylates to obtain fluorine-containing polymers with excellent properties. Acrylate copolymers containing fluorine branching have ultra-low surface tension and high oxygen permeability, low water absorption and high chemical resistance. Polymeric materials encyclopedia (Polymeric materials encyclopedia, Boca Raton: CRC Press. 1996.1536) introduces that fluorine-containing coatings give fabrics, paper, and leather surfaces water and oil repellency and stain resistance. There are two main synthetic routes for fluorinated acrylate monomers: (1) synthesized by fluorinated alcohols and (meth)acrylates; (2) synthesized by the reaction of perfluoroiodane and (meth)acrylate It is produced by companies such as 3M, Du Pont, Hoechst, Asahi Glass, Daikin Industries and Osaka Organic Chemicals. Research paper (Acta Polymer Sinica, 2002, 6:770-774) reported the reaction of perfluorooctanoic acid and hydroxypropyl methacrylate to synthesize perfluorooctanoyloxypropyl methacrylate, the surface energy of the fluorine-containing acrylate homopolymer It is 14.2mN/m. At present, the research on fluorine-containing acrylate monomers at home and abroad (Macromolecules, 1997, 30: 2883-2890; Macromolecules, 2002, 35: 1658-1662; Acta Polymer Sinica, 2004, (2): 196-200) mainly focuses on Perfluoroalkyl (C6 -C9 ) ethyl (meth)acrylate.
纳米二氧化硅的制备已有大量的文献和专利报道，Iler的专著(The Chemistry of Silica，Wiley&Sons，New York，1979)中第四章已有详细论述。由廉价的硅酸钠为原料，采用逐步增长法制备粒径可控的、球形、单分散稳定的纳米二氧化硅水溶胶。该方法工艺简单，制备时间短，已有研究报道(袁荞龙，应圣康，硅溶胶在水性聚氨酯中的流变性能，功能高分子学报，1997，10(4)，456～462)。将二氧化硅从水相转为有机相，已在Iler专著的第四、六章中有论述(Iler，R K，The Chemistry of Silica，Wiley&Sons，New York，1979)。美国专利(US5885485；US5902226)则发明了二氧化硅醇溶胶的制备。The preparation of nano-silica has a large amount of literature and patent reports, and the fourth chapter of Iler's monograph (The Chemistry of Silica, Wiley & Sons, New York, 1979) has been discussed in detail. Using cheap sodium silicate as raw material, the nano-silica hydrosol with controllable particle size, spherical shape and monodisperse stability was prepared by step-growth method. The method has simple process and short preparation time, and has been reported (Yuan Qiaolong, Ying Shengkang, Rheological properties of silica sol in waterborne polyurethane, Journal of Functional Polymers, 1997, 10(4), 456-462). The transformation of silica from an aqueous phase to an organic phase has been discussed in Chapters 4 and 6 of Iler's monograph (Iler, RK, The Chemistry of Silica, Wiley & Sons, New York, 1979). US patents (US5885485; US5902226) invented the preparation of silica alcohol sol.
无机微粒具有高强度、高硬度、热稳定性和化学稳定性，与韧性的有机聚合物复合，可充分发挥各自的优点，且可以获得两者不具备的特性。无机纳米微粒-有机聚合物形成杂化膜，该膜的硬度、耐磨性、耐刮擦性、耐热性、耐水性、耐候性、透湿性等性能大为提高。目前在制备有机聚合物-无机纳米复合材料时主要采用添加二氧化硅粉体的方法，尽管这类粉体材料的原生粒子粒径小于100nm，但其团聚尺寸远远超过100nm，一般都在微米数量级上，在涂料制备过程中无法再分散成为纳米级，难以体现出纳米材料的优势。考虑到纳米颗粒的比表面积大、表面能高，易于团聚。因此，制备纳米复合材料往往需要利用一些特殊的工艺。陈文昌等(Wen-Chang Chen，et al.Polymer，2003，44，593-601；Materials and Chemistry andPhysics，2003，82，388-395)报道了用硅烷偶联剂改性有机二氧化硅溶胶后与丙烯酸酯聚合物杂化，所得膜均匀，且光学透明性好，热稳定性增加，力学性能优于聚甲基丙烯酸甲酯膜，可作为无源膜用于光学器件。张启卫等(ZHANG Qi-Wei，ZHANG Yong-Hua，CHEN Shou-Ming等，Chin J Appl Chem，2002，19(9)：874)利用Sol-Gel技术制备出PMMA/nano-SiO2纳米复合材料，发现有机/无机两相间的相容性好，不产生相分离，材料透明性高，且杂化材料的热稳定性和玻璃化温度都有较大的提高。张晟卯(ZHANG Sheng-Mao(张晟卯)，GAO Yong-Jian(高永建)等，Chin J Appl Chem(应用化学)，2002，19(9)：914)利用紫外光照射引发原位聚合技术制备出SiO2/聚丙烯酸丁酯纳米复合膜，发现复合膜的摩擦性能显著改善，可以作为润滑材料使用。徐国财等(徐国财、马家举、邢宏龙，应用化学，2000，17(4)：450)用原位分散紫外光固化技术制备聚合物/纳米二氧化硅复合材料，发现复合材料的玻璃化温度有所提高。不仅如此，纳米复合材料的模量较聚合物本体提高了1倍以上。美国应用专利USPat20030050358报道了用溶胶-凝胶法制备出SiO2/聚氟化丙烯酸酯有机-无机杂化材料，这材料具有少量的光损失可以应用于电讯传输的过程中。韩国专利KR2003054349公开了由改性的乙烯基丙烯酸树脂作为胶粘剂，三聚氰胺或异氰酸酯作为固化剂，氟化烯烃基蜡为润滑剂，氧化硅为抗腐蚀剂配制成一种保护钢板的涂层溶液。日本公开特许公告JP2005008878公开了用硅烷偶联剂改性的氧化硅胶体改性甲基丙烯酸乙酯和异氰酸酯的二嵌段共聚物，通过UV固化可以得到一层具有良好耐磨性的坚硬的漆膜。中国发明专利(CN 1369511A)公开了一种“有机高分子-无机纳米材料构成的核-壳结构杂化体”的制备方法，无机纳米微粒与有机聚合物形成核-壳型结构的杂化材料提高材料的性能，详细描述了由直接分散聚合法制备水性纳米二氧化硅及其复合微粒-α烯烃及共轭二烯烃聚合物杂化胶乳的方法。Inorganic particles have high strength, high hardness, thermal stability and chemical stability, and when combined with tough organic polymers, they can give full play to their respective advantages, and can obtain characteristics that the two do not have. Inorganic nanoparticles-organic polymers form a hybrid film, and the hardness, wear resistance, scratch resistance, heat resistance, water resistance, weather resistance, moisture permeability and other properties of the film are greatly improved. At present, the method of adding silica powder is mainly used in the preparation of organic polymer-inorganic nanocomposites. Although the primary particle size of this type of powder material is less than 100nm, its agglomeration size far exceeds 100nm, generally in the micron On the order of magnitude, it can no longer be dispersed into nanoscale during the coating preparation process, and it is difficult to reflect the advantages of nanomaterials. Considering the large specific surface area and high surface energy of nanoparticles, they are easy to agglomerate. Therefore, the preparation of nanocomposites often requires the use of some special processes. Chen Wenchang et al. (Wen-Chang Chen, et al.Polymer, 2003,44,593-601; Materials and Chemistry and Physics, 2003,82,388-395) reported that after modifying organosilica sol with silane coupling agent and Acrylate polymer hybridization, the obtained film is uniform, and has good optical transparency, increased thermal stability, and better mechanical properties than polymethyl methacrylate film, and can be used as a passive film for optical devices. Zhang Qiwei etc. (ZHANG Qi-Wei, ZHANG Yong-Hua, CHEN Shou-Ming etc., Chin J Appl Chem, 2002,19 (9): 874) utilize Sol-Gel technology to prepare PMMA/nano-SiO Nanocomposite material, It is found that the compatibility between the organic/inorganic two phases is good, no phase separation occurs, the material has high transparency, and the thermal stability and glass transition temperature of the hybrid material are greatly improved. Zhang Shengmao (ZHANG Sheng-Mao (Zhang Shengmao), GAO Yong-Jian (Gao Yongjian), etc., Chin J Appl Chem (Applied Chemistry), 2002, 19 (9): 914) uses ultraviolet light irradiation to initiate in-situ polymerization technology The SiO2 /polybutylacrylate nanocomposite film was prepared, and it was found that the friction performance of the composite film was significantly improved, and it could be used as a lubricating material. Xu Guocai et al. (Xu Guocai, Ma Jiaju, Xing Honglong, Applied Chemistry, 2000, 17(4): 450) prepared polymer/nano-silicon dioxide composite materials with in-situ dispersion UV curing technology, and found that the glass transition temperature of the composite materials has increased . Not only that, the modulus of the nanocomposite is more than double that of the polymer itself. The US application patent USPat20030050358 reported the preparation of SiO2 / polyfluorinated acrylate organic-inorganic hybrid material by sol-gel method. This material has a small amount of light loss and can be applied in the process of telecommunication transmission. Korean patent KR2003054349 discloses a coating solution for protecting steel plates formulated with modified vinyl acrylic resin as an adhesive, melamine or isocyanate as a curing agent, fluorinated olefin-based wax as a lubricant, and silicon oxide as an anti-corrosion agent. Japanese Patent Publication JP2005008878 discloses a diblock copolymer of ethyl methacrylate and isocyanate modified by silica colloid modified with a silane coupling agent, and a layer of hard paint with good abrasion resistance can be obtained by UV curing membrane. Chinese invention patent (CN 1369511A) discloses a preparation method of a "core-shell structure hybrid composed of organic polymer-inorganic nanomaterials", a hybrid material with a core-shell structure formed by inorganic nanoparticles and organic polymers To improve the performance of materials, the method of preparing water-based nano silicon dioxide and its composite particles-alpha olefin and conjugated diene polymer hybrid latex by direct dispersion polymerization is described in detail.
本发明通过合适的工艺条件从由廉价的硅酸钠原料制备的单分散球形二氧化硅水溶胶转为粒径均匀、分散稳定的纳米二氧化硅有机溶胶，并合成一新的含氟丙烯酸酯，与丙烯酸酯共聚合形成含氟丙烯酸酯-二氧化硅杂化材料，使纳米二氧化硅颗粒在含氟丙烯酸酯体系中均匀、稳定的分散，改善丙烯酸酯树酯的性能，降低该树脂的表面能。The present invention transforms monodisperse spherical silica hydrosol prepared from cheap sodium silicate raw material into nano silica organosol with uniform particle size and stable dispersion through suitable process conditions, and synthesizes a new fluorine-containing acrylate , copolymerized with acrylate to form a fluorine-containing acrylate-silica hybrid material, so that nano-silica particles can be uniformly and stably dispersed in the fluorine-containing acrylate system, improve the performance of acrylate resin, and reduce the resin's surface energy.
发明内容Contents of the invention
本发明的单分散球形二氧化硅粒子的数均粒径为45nm，是由廉价的硅酸钠为原料，采用逐步增长法制备。该方法工艺简单，制备时间短，所得纳米二氧化硅为球形、单分散稳定的水溶胶。由全氟辛酸和(甲基)丙烯酸羟烷基酯合成新的含氟丙烯酸酯单体-(甲基)丙烯酸全氟辛酰氧基烷基酯的方法，是用有机合成化学中所知的酰氯化反应和酯化反应，在ChemicalReciew杂志1953年第52期中第237-416页有关于酰氯化反应的详细介绍。The number-average particle diameter of the monodisperse spherical silicon dioxide particles of the present invention is 45nm, and is prepared from cheap sodium silicate by adopting a step-by-step growth method. The method has simple process and short preparation time, and the obtained nano silicon dioxide is a spherical, monodisperse and stable aqueous sol. The method for synthesizing new fluorine-containing acrylate monomer-perfluorooctanoyloxyalkyl (meth)acrylate by perfluorooctanoic acid and hydroxyalkyl (meth)acrylate is to use acid chloride known in organic synthetic chemistry Reaction and esterification reaction, in ChemicalReciew magazine No. 52 in 1953, pages 237-416 have a detailed introduction about the acid chloride reaction.
纳米二氧化硅用硅烷偶联剂表面改性后能均匀分散于含氟丙烯酸酯树脂中。利用纳米颗粒比表面积大，纳米颗粒与树脂之间强大的界面结合力，可以提高涂层的强度、硬度、耐磨性、耐刮伤性等，纳米二氧化硅在膜表面可在纳米尺度上增加膜表面的粗糙度，使液体在膜表面无法在热力学上进行浸润铺展，有效提高膜的表面性能。而且由于纳米颗粒对可见光可透，可以保证涂层的透明性。本发明的目的是在传统的丙烯酸酯涂料的基础上，开发一种含氟丙烯酸酯-二氧化硅杂化材料的制备工艺，使得到的产物成膜后可以在材料表面，尤其是在无机材料表面形成具有良好的附着力，高硬度、高耐磨性和耐刮擦性，并同时具有低表面能而具有好的抗污性。Nano silicon dioxide can be uniformly dispersed in fluorine-containing acrylate resin after surface modification with silane coupling agent. Utilizing the large specific surface area of nanoparticles and the strong interfacial bonding force between nanoparticles and resin, the strength, hardness, wear resistance, scratch resistance, etc. of the coating can be improved. Increase the roughness of the membrane surface so that the liquid cannot thermodynamically infiltrate and spread on the membrane surface, effectively improving the surface performance of the membrane. And because the nanoparticles are transparent to visible light, the transparency of the coating can be guaranteed. The purpose of the present invention is on the basis of traditional acrylate paint, develops a kind of preparation technology of fluorine-containing acrylate-silicon dioxide hybrid material, makes the obtained product can be on the surface of the material, especially on the inorganic material after forming a film. The surface is formed with good adhesion, high hardness, high wear resistance and scratch resistance, and at the same time has low surface energy and good stain resistance.
本发明是通过以下的技术方案来实现：The present invention is achieved through the following technical solutions:
(1)全氟辛酸和二氯亚砜(SOCl2)回流反应后，减压蒸馏收集得到透明有强烈刺激性气味的全氟辛酰氯。在室温下将(甲基)丙烯酸羟烷基酯溶于THF中与全氟辛酰氯和少量三乙胺的THF溶液反应。将产物加入无水乙醚和NaOH水溶液，分离出的有机层用蒸馏水洗涤三次，然后通过水泵抽除溶剂，得到(甲基)丙烯酸羟烷基酯和(甲基)丙烯酸全氟辛酰氧基烷基酯(FA)浅黄色透明混合液体，其中FA的含量大于80％质量比。(1) After reflux reaction between perfluorooctanoic acid and thionyl chloride (SOCl2 ), transparent perfluorooctanoyl chloride with a strong pungent smell was collected by distillation under reduced pressure. Hydroxyalkyl (meth)acrylate was dissolved in THF to react with a THF solution of perfluorooctanoyl chloride and a small amount of triethylamine at room temperature. The product was added to anhydrous ether and NaOH aqueous solution, the separated organic layer was washed three times with distilled water, and then the solvent was removed by a water pump to obtain hydroxyalkyl (meth)acrylate and perfluorooctanoyloxyalkane (meth)acrylate FA is a light yellow transparent mixed liquid, wherein the content of FA is greater than 80% by mass.
(2)将固含量为5～30wt％的、数均粒径为45nm的二氧化硅水溶胶在常压、室温的条件下进行纯化处理，得到的二氧化硅水溶胶与有机溶剂混合，通过共沸蒸馏或离心分离的方法除去其中的水，形成均一、半透明的纳米二氧化硅有机溶胶。(2) Purify the silicon dioxide hydrosol with a solid content of 5 to 30 wt % and a number average particle diameter of 45 nm at normal pressure and room temperature, mix the obtained silicon dioxide water sol with an organic solvent, and pass The method of azeotropic distillation or centrifugation removes the water in it to form a uniform and translucent nano-silica organosol.
(3)将1～50％质量比(以二氧化硅的量为基准)的硅烷偶联剂作表面改性剂，在有机溶胶的回流温度下，强烈搅拌的条件下，加到有机硅溶胶中，反应3～15小时。得到表面改性的氧化硅有机溶胶。作纳米二氧化硅表面改性剂的硅烷偶联剂的分子结构式如下：(3) The silane coupling agent with a mass ratio of 1 to 50% (based on the amount of silicon dioxide) is used as a surface modifier, and is added to the organosilicon sol under the condition of strong stirring at the reflux temperature of the organosol , react for 3 to 15 hours. A surface-modified silica organosol is obtained. The molecular structural formula of the silane coupling agent used as nano-silica surface modifier is as follows:
Y-R-SiX3YR-SiX3
Y是乙烯基、羟基、氨烷基、氨基、环氧基或巯基；X是包括甲氧基、乙氧基、丙氧基、异丙氧基、乙酰氧基在内的一切可水解有机基团；R为0至3个碳原子的直链烷烃基。主要指乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β甲氧基乙氧)基硅烷、N-β-(胺乙基)-γ胺丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷、γ-(甲基丙烯酰胺氧基)丙基三甲氧基硅烷、γ-硫醇基丙基三甲氧基硅烷。Y is vinyl, hydroxyl, aminoalkyl, amino, epoxy or mercapto; X is all hydrolyzable organic groups including methoxy, ethoxy, propoxy, isopropoxy, acetoxy Group; R is a linear alkane group of 0 to 3 carbon atoms. Mainly refers to vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(βmethoxyethoxy)silane, N-β-(aminoethyl)-γaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(methacrylamidooxy)propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane.
(4)将各种丙烯酸酯单体(丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸、甲基丙烯酸)和苯乙烯，引发剂、硫醇、所得到的纳米二氧化硅有机溶胶及含氟丙烯酸酯单体等按照一定比例混合均匀。在50～90℃，氮气保护并搅拌的条件下，于1～6小时内均匀滴加到反应溶剂中。在反应加料完毕前1～30分钟时，一次性注入功能单体(含氟丙烯酸酯)。滴加完毕后，补加少量的引发剂，保温0.5～2小时，结束反应。得到稳定的、透明且略带有荧光的树脂。杂化丙烯酸酯材料中加入的含氟丙烯酸酯单体为0.5～20％质量比，纳米二氧化硅的含量为0.5～15％质量比。(4) Various acrylate monomers (ethyl acrylate, butyl acrylate, isooctyl acrylate, butyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid, Methacrylic acid) and styrene, initiator, mercaptan, obtained nano-silica organosol and fluorine-containing acrylate monomer etc. are uniformly mixed according to a certain ratio. At 50-90°C, under the condition of nitrogen protection and stirring, it is evenly added dropwise into the reaction solvent within 1-6 hours. 1 to 30 minutes before the completion of the reaction feeding, inject the functional monomer (fluorine-containing acrylate) at one time. After the dropwise addition is completed, add a small amount of initiator and keep warm for 0.5 to 2 hours to end the reaction. A stable, transparent and slightly fluorescent resin was obtained. The fluorine-containing acrylate monomer added to the hybrid acrylate material is 0.5-20% by mass, and the content of nano silicon dioxide is 0.5-15% by mass.
本发明提供的制备方法，合成了分子量为7000～30000的丙烯酸酯树脂。其中采用的二氧化硅水溶胶的粒径可为5～100nm。二氧化硅有机溶胶制备过程中的有机溶剂包括丁酮、戊酮、丁醚、异戊醚、丙醇、丁醇、甲苯、辛烷、吡啶中一种或几种的混合溶剂等。含氟丙烯酸酯单体除上述的(甲基)丙烯酸-β-全氟辛酰氧基-烷基酯外，还可以是丙烯酸-1，1-二氢代全氟丁酯、(甲基)丙烯酸全氟烷基酯、(甲基)丙烯酸全氟烷基(C6～C9)乙酯、(甲基)丙烯酸全氟酰胺酯。在树脂合成中选择的有机溶剂可以是氟代苯、六氟代苯、1，2-二氟-1，1，2，2-四氯乙烷、三氟甲苯、丁酮、戊酮、苯、甲苯、二甲苯、辛烷、吡啶、N-甲基吡啶、吡咯烷酮、N-甲基吡咯烷酮中一种或几种的混合物。According to the preparation method provided by the invention, the acrylate resin with a molecular weight of 7000-30000 is synthesized. The particle size of the silica hydrosol used therein may be 5-100 nm. The organic solvent in the preparation process of the silica organosol includes butanone, pentanone, butyl ether, isoamyl ether, propanol, butanol, toluene, octane, pyridine or a mixed solvent of several kinds thereof. In addition to the above-mentioned (meth)acrylic acid-β-perfluorooctanoyloxy-alkyl ester, the fluorine-containing acrylate monomer can also be acrylate-1,1-dihydroperfluorobutyl ester, (methyl) Perfluoroalkyl acrylate, perfluoroalkyl (C6 -C9 ) ethyl (meth)acrylate, perfluoroamide (meth)acrylate. The organic solvent selected in resin synthesis can be fluorobenzene, hexafluorobenzene, 1,2-difluoro-1,1,2,2-tetrachloroethane, trifluorotoluene, methyl ethyl ketone, pentanone, benzene , toluene, xylene, octane, pyridine, N-picoline, pyrrolidone, N-methylpyrrolidone or a mixture of several.
该种方法制得的含氟丙烯酸酯-二氧化硅杂化材料的硬度按GB1730-82测试，耐磨性按GB1768-79测试，附着力按GB1720-79测试，对水的接触角用上海中晨数字技术设备有限公司的JC2000A接触角测量仪上测水-杂化膜的接触角。The hardness of the fluorine-containing acrylate-silicon dioxide hybrid material prepared by this method is tested according to GB1730-82, the abrasion resistance is tested according to GB1768-79, the adhesion is tested according to GB1720-79, and the contact angle to water is tested by Shanghai Zhong The contact angle of the water-hybrid film was measured on the JC2000A contact angle measuring instrument of Chen Digital Technology Equipment Co., Ltd.
具体实施方式Detailed ways
实例1Example 1
全氟辛酸和SOCl2在70～80℃之间回流反应后，减压蒸馏收集30～40℃之间的馏分，得到透明有强烈刺激性气味的全氟辛酰氯。在室温下将3.9g甲基丙烯酸羟乙酯(HEMA)溶于THF中加入到100mL三口烧瓶中，搅拌下将13.0g全氟辛酰氯和少量三乙胺的THF溶液加入烧瓶中，加热到35℃继续反应3h。将产物加入50mL无水乙醚和NaOH水溶液，分离出的有机层用蒸馏水洗涤三次，然后通过水泵抽除溶剂，得到浅黄色透明的HEMA和甲基丙烯酸全氟辛酰氧基乙酯(FA)的混合液体，其中FA含量大于80％质量比。After the reflux reaction between perfluorooctanoic acid and SOCl2 at 70-80°C, the fraction between 30-40°C was collected by vacuum distillation to obtain transparent perfluorooctanoyl chloride with a strong pungent smell. Dissolve 3.9g of hydroxyethyl methacrylate (HEMA) in THF at room temperature and add it to a 100mL three-necked flask, add a THF solution of 13.0g perfluorooctanoyl chloride and a small amount of triethylamine to the flask under stirring, and heat to 35 ° C to continue the reaction for 3h. The product was added to 50 mL of anhydrous ether and NaOH aqueous solution, and the separated organic layer was washed three times with distilled water, and then the solvent was removed by a water pump to obtain light yellow transparent HEMA and perfluorooctanoyloxyethyl methacrylate (FA). The mixed liquid, wherein the FA content is greater than 80% by mass.
实例2Example 2
在搅拌下，5小时内向100ml二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)中连续滴加500ml的正丙醇，同时进行减压蒸馏。取3克乙烯基三异丙氧基硅烷与3g的丙醇混合均匀，在95℃剧烈搅拌条件下，于3小时内滴加到二氧化硅醇溶胶中，然后继续反应1小时得到改性的二氧化硅有机溶胶。将各种单体(15g丙烯酸，75g丙烯酸丁酯，40g甲基丙烯酸羟乙酯，70g甲基丙烯酸甲酯，50g苯乙烯)和硫醇、BPO及20g纳米二氧化硅有机溶胶混合均匀。在氮气保护下，100℃时将上诉混合物于3小时内滴加到150ml三氟甲苯与二甲苯(1∶1)的混合溶剂中，在滴加完毕前5分钟注入5g甲基丙烯酸全氟辛基乙酯。反应1小时后补加0.6gBPO，继续保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料，其膜的硬度0.9，耐磨性0.006，附着力1级，对水的接触角为104°。Under stirring, 500ml of n-propanol was continuously added dropwise to 100ml of silica hydrosol (solid content: 15wt%, number average particle diameter: 45nm) within 5 hours, and vacuum distillation was carried out simultaneously. Take 3 grams of vinyl triisopropoxysilane and 3 g of propanol, mix them evenly, and add them dropwise to the silica alcohol sol within 3 hours under the condition of vigorous stirring at 95 ° C, and then continue to react for 1 hour to obtain the modified Silica organosol. Mix various monomers (15g acrylic acid, 75g butyl acrylate, 40g hydroxyethyl methacrylate, 70g methyl methacrylate, 50g styrene) with mercaptan, BPO and 20g nano-silica organic sol. Under nitrogen protection, at 100°C, add the above-mentioned mixture dropwise to 150ml of a mixed solvent of trifluorotoluene and xylene (1:1) within 3 hours, and inject 5g of perfluorooctyl methacrylate 5 minutes before the completion of the dropwise addition. ethyl ethyl ester. After reacting for 1 hour, add 0.6g of BPO, continue to keep warm for 2 hours, and lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano-silicon dioxide. The contact angle was 104°.
实例3Example 3
在搅拌下，5小时内向100ml纯化后的二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)中连续滴加200ml的2-甲基吡咯烷酮，同时进行减压蒸馏，除去体系中的水，得到有机溶胶。将各种单体(10g丙烯酸，85g丙烯酸乙酯，40g甲基丙烯酸羟乙酯，75g甲基丙烯酸甲酯，45g苯乙烯)和硫醇、AIBN及20g纳米二氧化硅有机溶胶，1g乙烯基三异丙氧基硅烷混合均匀。在氮气的保护下85℃时，于4小时内均匀滴入150ml三氟甲苯中，在滴加完毕前3～7分钟时一次性加入10g甲基丙烯酸全氟辛酰氧丙基酯。反应一小时后补加1gAIBN，继续保温0.5小时后降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料。其膜的硬度为0.92，耐磨性0.007，附着力1级，对水的接触角108°。Under stirring, 200ml of 2-methylpyrrolidone was continuously added dropwise to 100ml of purified silica hydrosol (solid content: 15wt%, number average particle diameter: 45nm) within 5 hours, and vacuum distillation was carried out simultaneously to remove the system in water to obtain an organosol. Various monomers (10g acrylic acid, 85g ethyl acrylate, 40g hydroxyethyl methacrylate, 75g methyl methacrylate, 45g styrene) and thiol, AIBN and 20g nano-silica organosol, 1g vinyl Triisopropoxysilane mixed well. Under the protection of nitrogen, at 85°C, evenly drop into 150ml of trifluorotoluene within 4 hours, and add 10g of perfluorooctanoyloxypropyl methacrylate at one time 3 to 7 minutes before the completion of the dropwise addition. After reacting for one hour, add 1g of AIBN, continue to keep warm for 0.5 hours, and then lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano silicon dioxide. The hardness of the film is 0.92, the abrasion resistance is 0.007, the adhesion is grade 1, and the contact angle to water is 108°.
实例4Example 4
将200ml的丁醚与60ml的二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)混合，在搅拌的条件下进行减压蒸馏，除去体系中的水形成氧化硅的丁醚分散液。将各种单体(10g甲基丙烯酸，60g甲基丙烯酸正辛酯，40g甲基丙烯酸羟乙酯，85g甲基丙烯酸甲酯，50g苯乙烯)和硫醇、AIBN及15g上诉有机溶胶，3gγ-氨基丙基三乙氧基硅烷混合均匀。在氮气的保护下85℃时，于4小时内均匀滴入150ml1，2-二氟-1，1，2，2-四氯乙烷与辛烷(2∶1)的混合溶剂中，在滴加完毕前5分钟时一次性加入15g甲基丙烯酸-β-全氟辛酰氧基-乙酯。反应1小时后补加0.6gBPO，继续保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料。其膜的硬度为0.88，耐磨性0.009，附着力1级，对水的接触角105°。Mix 200ml of butyl ether with 60ml of silicon dioxide hydrosol (solid content is 15wt%, number average particle diameter is 45nm), carry out vacuum distillation under the condition of stirring, remove the water in the system to form butyl ether of silicon oxide Dispersions. Various monomers (10g methacrylic acid, 60g n-octyl methacrylate, 40g hydroxyethyl methacrylate, 85g methyl methacrylate, 50g styrene) and mercaptan, AIBN and 15g appeal organosol, 3gγ -Aminopropyltriethoxysilane Mix well. Under the protection of nitrogen, at 85°C, within 4 hours, evenly drop 150ml of 1,2-difluoro-1,1,2,2-tetrachloroethane and octane (2:1) in the mixed solvent. Five minutes before the completion of the addition, 15 g of methacrylic acid-β-perfluorooctanoyloxy-ethyl ester was added in one go. After reacting for 1 hour, add 0.6 g of BPO, continue to keep warm for 2 hours, and lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano silicon dioxide. The hardness of the film is 0.88, the abrasion resistance is 0.009, the adhesion is grade 1, and the contact angle to water is 105°.
实例5Example 5
将500ml戊酮与100ml二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)混合，在83℃搅拌的条件下进行蒸馏，除去体系中的水，形成均一、稳定的纳米二氧化硅戊酮分散液。3g乙烯基三甲氧基硅烷加到制得的二氧化硅酮分散液中搅拌均匀，在90℃的条件下，反应10小时得到改性的有机溶胶。将各种单体(25g丙烯酸，65g丙烯酸正丁酯，50g甲基丙烯酸羟乙酯，80g甲基丙烯酸甲酯，60g苯乙烯)和硫醇、AIBN及20g上诉纳米二氧化硅有机溶胶混合均匀。在氮气保护下，90℃时将上诉混合物于3小时内滴加到150ml氟代苯和甲苯(3∶1)的混合溶剂中，在滴加完毕前25分钟注入20g丙烯酸-1，1-二氢代全氟丁酯。反应1小时后补加1gBPO，再保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料。其膜的硬度0.91，耐磨性0.007，附着力1级，对水的接触角104°。Mix 500ml of pentanone with 100ml of silica hydrosol (solid content is 15wt%, number average particle diameter is 45nm), distilled under the condition of stirring at 83 ℃, remove the water in the system, form uniform, stable nanometer Silica Pentanone Dispersion. Add 3 g of vinyltrimethoxysilane to the prepared silicone dioxide dispersion, stir evenly, and react at 90° C. for 10 hours to obtain a modified organosol. Mix various monomers (25g acrylic acid, 65g n-butyl acrylate, 50g hydroxyethyl methacrylate, 80g methyl methacrylate, 60g styrene) with mercaptan, AIBN and 20g appealing nano-silica organosol . Under nitrogen protection, at 90°C, add the above-mentioned mixture dropwise to 150ml of a mixed solvent of fluorobenzene and toluene (3:1) within 3 hours, and inject 20g of acrylic acid-1,1-dimethoxylate 25 minutes before the completion of the dropwise addition. Hydrogenated perfluorobutyl ester. After reacting for 1 hour, add 1 g of BPO, keep the temperature for another 2 hours, and lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano silicon dioxide. The hardness of the film is 0.91, the abrasion resistance is 0.007, the adhesion is grade 1, and the contact angle to water is 104°.
实例6Example 6
将100ml乙醇与100ml的二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)混合，在10000转/分钟的条件下进行离心分离，弃去上层清液后，重复上诉操作9次，得到稳定均匀的纳米二氧化硅醇分散液。取3克乙烯基三乙氧基硅烷与3的乙醇混合均匀，在78℃，剧烈搅拌条件下，于3小时内滴加到制得的醇溶胶中，然后继续反应1小时得到改性的纳米二氧化硅有机溶胶。将各种单体(45g丙烯酸，55g甲基丙烯酸正辛酯，40g甲基丙烯酸羟乙酯，70g甲基丙烯酸甲酯，60g苯乙烯)和硫醇、BPO及20g上诉纳米二氧化硅有机溶胶混合均匀。在氮气保护下，100℃时将上诉混合物于3小时内滴加到150ml三氟甲苯中，在滴加完毕前5分钟注入15g甲基丙烯酸-β-全氟辛酰氧基-乙酯。反应1小时后补加1.5gBPO，继续保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料。其膜的硬度为0.91，耐磨性0.008，附着力1级，对水的接触角107°。Mix 100ml of ethanol with 100ml of silica hydrosol (solid content is 15wt%, number average particle diameter is 45nm), centrifuge under the condition of 10000 rpm, after discarding the supernatant, repeat the appeal operation 9 Once, a stable and uniform nano-silica alcohol dispersion is obtained. Take 3 grams of vinyltriethoxysilane and 3% ethanol, mix it evenly, and add it dropwise to the prepared alcohol sol within 3 hours at 78°C under vigorous stirring, and then continue to react for 1 hour to obtain the modified nano Silica organosol. Various monomers (45g acrylic acid, 55g n-octyl methacrylate, 40g hydroxyethyl methacrylate, 70g methyl methacrylate, 60g styrene) and mercaptan, BPO and 20g appeal nano-silica organic sol well mixed. Under the protection of nitrogen, the above mixture was added dropwise to 150ml of trifluorotoluene at 100°C within 3 hours, and 15g of methacrylic acid-β-perfluorooctanoyloxy-ethyl ester was injected 5 minutes before the completion of the dropwise addition. After reacting for 1 hour, add 1.5 g of BPO, continue to keep warm for 2 hours, and lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano silicon dioxide. The hardness of the film is 0.91, the abrasion resistance is 0.008, the adhesion is grade 1, and the contact angle to water is 107°.
实例7Example 7
将100ml丁醚与100ml的二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)混合，在8000转/分钟的条件下进行离心分离，弃去上层清液后，重复上诉操作9次，得到稳定均匀的纳米二氧化硅醚分散液。将各种反应物(10g甲基丙烯酸，60g甲基丙烯酸正辛酯，40g甲基丙烯酸羟乙酯，85g甲基丙烯酸甲酯，50g苯乙烯)和硫醇、AIBN及15g上诉纳米二氧化硅有机溶胶，3g γ-氨基丙基三乙氧基硅烷混合均匀。在氮气保护下，65℃时将上诉混合物于3小时内滴加到150ml三氟甲苯中，在滴加完毕前5分钟注入15g甲基丙烯酸-β-全氟辛酰氧基-乙酯。反应1小时后补加1.5gBPO，继续保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料。其膜的硬度为0.91，耐磨性0.008，附着力1级，对水的接触角105°。Mix 100ml of butyl ether with 100ml of silica hydrosol (solid content is 15wt%, number average particle diameter is 45nm), centrifuge under the condition of 8000 rpm, after discarding the supernatant, repeat the appeal operation 9 times to obtain a stable and uniform nano-silica ether dispersion. Various reactants (10g methacrylic acid, 60g n-octyl methacrylate, 40g hydroxyethyl methacrylate, 85g methyl methacrylate, 50g styrene) and mercaptan, AIBN and 15g appeal to nano silicon dioxide Organosol, 3g γ-aminopropyltriethoxysilane were mixed evenly. Under the protection of nitrogen, the above-mentioned mixture was added dropwise to 150 ml of trifluorotoluene at 65° C. within 3 hours, and 15 g of methacrylic acid-β-perfluorooctanoyloxy-ethyl ester was injected 5 minutes before the completion of the dropwise addition. After reacting for 1 hour, add 1.5 g of BPO, continue to keep warm for 2 hours, and lower the temperature to obtain a hybrid material of fluorine-containing acrylate and nano silicon dioxide. The hardness of the film is 0.91, the abrasion resistance is 0.008, the adhesion is grade 1, and the contact angle to water is 105°.
实例8Example 8
将100ml丁酮与100ml的二氧化硅水溶胶(固含量为15wt％，数均粒径为45nm)混合，在8500转/分钟的条件下进行离心分离，弃去上层清液后，重复上诉操作10次，得到稳定均匀的纳米二氧化硅酮分散液。取3克乙烯基三乙氧基硅烷与3g的丁酮混合均匀，在85℃，剧烈搅拌条件下，于3小时内滴加到制得的纳米二氧化硅酮溶胶中，然后继续反应1小时得到改性的有机溶胶。将各种单体(17g丙烯酸，70g丙烯酸丁酯，38g甲基丙烯酸羟乙酯，75g甲基丙烯酸甲酯，50g苯乙烯)和硫醇、BPO及20g上诉纳米二氧化硅有机溶胶混合均匀。在氮气保护下，100℃时将上诉混合物于3小时内滴加到150ml三氟甲苯中，在滴加完毕前5分钟注入9g丙烯酸全氟辛基乙酯。反应1小时后补加0.6gBPO，继续保温2小时，降温，得到含氟丙烯酸酯与纳米二氧化硅的杂化材料，其膜的硬度为0.91，耐磨性0.007，附着力1级，对水的接触角104°。Mix 100ml methyl ethyl ketone with 100ml silica hydrosol (solid content is 15wt%, number average particle diameter is 45nm), carry out centrifugation under the condition of 8500 rev/mins, after discarding the supernatant, repeat the appeal operation 10 times to obtain a stable and uniform dispersion of nano-silica. Take 3 grams of vinyl triethoxysilane and 3 g of methyl ethyl ketone, mix them evenly, and add them dropwise to the prepared nano-silica sol within 3 hours at 85 ° C under vigorous stirring, and then continue to react for 1 hour A modified organosol is obtained. Mix various monomers (17g acrylic acid, 70g butyl acrylate, 38g hydroxyethyl methacrylate, 75g methyl methacrylate, 50g styrene) with mercaptan, BPO and 20g of nano-silica organosol. Under the protection of nitrogen, the above-mentioned mixture was added dropwise to 150 ml of trifluorotoluene at 100° C. within 3 hours, and 9 g of perfluorooctylethyl acrylate was injected 5 minutes before the completion of the dropwise addition. After reacting for 1 hour, add 0.6g of BPO, continue to keep warm for 2 hours, and cool down to obtain a hybrid material of fluorine-containing acrylate and nano-silicon dioxide. The contact angle is 104°.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610023821CN1824699A (en) | 2006-02-10 | 2006-02-10 | A method for reducing the surface energy of acrylate materials |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610023821CN1824699A (en) | 2006-02-10 | 2006-02-10 | A method for reducing the surface energy of acrylate materials |
| Publication Number | Publication Date |
|---|---|
| CN1824699Atrue CN1824699A (en) | 2006-08-30 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610023821PendingCN1824699A (en) | 2006-02-10 | 2006-02-10 | A method for reducing the surface energy of acrylate materials |
| Country | Link |
|---|---|
| CN (1) | CN1824699A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177485B (en)* | 2007-10-31 | 2010-06-23 | 大连理工大学 | Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same |
| CN101824273A (en)* | 2010-03-31 | 2010-09-08 | 中科院广州化学有限公司 | Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof |
| CN102086333A (en)* | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102086246A (en)* | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
| CN101469922B (en)* | 2007-12-27 | 2011-11-16 | Tcl集团股份有限公司 | Condenser for outdoor unit of air conditioner and method for producing the same |
| CN102321415A (en)* | 2011-08-11 | 2012-01-18 | 天津大学 | Fluorine-silicon acrylic resin nano composite anti-icing coating and preparation method thereof |
| CN102381000A (en)* | 2010-09-06 | 2012-03-21 | Jsr株式会社 | Curable composition and anti-reflective laminate |
| CN102952360A (en)* | 2012-11-06 | 2013-03-06 | 浙江国威汽车配件有限公司 | Fluorine-containing polymer mixing material and method for preparing bulb buffer ball keyway by same |
| CN103289014A (en)* | 2013-06-13 | 2013-09-11 | 江苏中恒宠物用品股份有限公司 | Synthetic method of stain-resistant cloth surface treating agent |
| CN103709800A (en)* | 2013-11-19 | 2014-04-09 | 北京化工大学常州先进材料研究院 | High glass adhesion UV (ultraviolet) resin |
| CN104262151A (en)* | 2014-09-19 | 2015-01-07 | 广东希贵光固化材料有限公司 | Fluorine-containing photocuring monomer and preparation method thereof |
| CN105315874A (en)* | 2015-12-05 | 2016-02-10 | 中国航空工业集团公司洛阳电光设备研究所 | Paint coat protecting nano coating, paint coat protecting method and airborne optoelectronic pod |
| CN107099188A (en)* | 2017-06-09 | 2017-08-29 | 浙江银鹿新材料有限公司 | A kind of snowflake printing ink of toughened antiwear and preparation method thereof |
| CN109651915A (en)* | 2018-12-03 | 2019-04-19 | 中建七局建筑装饰工程有限公司 | A kind of super-hydrophobic acrylic coating of antistatic, preparation method and applications |
| CN111777936A (en)* | 2020-07-03 | 2020-10-16 | 江苏新光镭射包装材料股份有限公司 | Scratch-resistant fingerprint-resistant touch decorative film and preparation process thereof |
| CN112143322A (en)* | 2020-09-04 | 2020-12-29 | 浙江玖龙新材料有限公司 | Formula and preparation method of high-self-leveling acrylic emulsion |
| CN113416459A (en)* | 2021-06-11 | 2021-09-21 | 安徽强邦新材料股份有限公司 | Printing plate protective coating and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177485B (en)* | 2007-10-31 | 2010-06-23 | 大连理工大学 | Low surface-energy fluorosiloxane containing double parallel main-chain structure and method for synthesizing the same |
| CN101469922B (en)* | 2007-12-27 | 2011-11-16 | Tcl集团股份有限公司 | Condenser for outdoor unit of air conditioner and method for producing the same |
| CN101824273A (en)* | 2010-03-31 | 2010-09-08 | 中科院广州化学有限公司 | Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof |
| CN101824273B (en)* | 2010-03-31 | 2013-01-09 | 中科院广州化学有限公司 | Fluoropolymer/inorganic nano-hybrid particle modified ultraviolet photocured paint and preparation method thereof |
| CN102381000A (en)* | 2010-09-06 | 2012-03-21 | Jsr株式会社 | Curable composition and anti-reflective laminate |
| CN102381000B (en)* | 2010-09-06 | 2015-11-25 | Jsr株式会社 | Solidification compound and anti-reflective laminate |
| CN102086333B (en)* | 2010-11-29 | 2013-04-03 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102086333A (en)* | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Organic-inorganic composite coating in chrysanthemum-shaped micro-nano structure and preparation method thereof |
| CN102086246A (en)* | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
| CN102086246B (en)* | 2010-11-29 | 2012-12-26 | 江苏足迹涂料有限公司 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
| CN102321415A (en)* | 2011-08-11 | 2012-01-18 | 天津大学 | Fluorine-silicon acrylic resin nano composite anti-icing coating and preparation method thereof |
| CN102952360A (en)* | 2012-11-06 | 2013-03-06 | 浙江国威汽车配件有限公司 | Fluorine-containing polymer mixing material and method for preparing bulb buffer ball keyway by same |
| CN103289014A (en)* | 2013-06-13 | 2013-09-11 | 江苏中恒宠物用品股份有限公司 | Synthetic method of stain-resistant cloth surface treating agent |
| CN103709800A (en)* | 2013-11-19 | 2014-04-09 | 北京化工大学常州先进材料研究院 | High glass adhesion UV (ultraviolet) resin |
| CN104262151A (en)* | 2014-09-19 | 2015-01-07 | 广东希贵光固化材料有限公司 | Fluorine-containing photocuring monomer and preparation method thereof |
| CN105315874A (en)* | 2015-12-05 | 2016-02-10 | 中国航空工业集团公司洛阳电光设备研究所 | Paint coat protecting nano coating, paint coat protecting method and airborne optoelectronic pod |
| CN107099188A (en)* | 2017-06-09 | 2017-08-29 | 浙江银鹿新材料有限公司 | A kind of snowflake printing ink of toughened antiwear and preparation method thereof |
| CN109651915A (en)* | 2018-12-03 | 2019-04-19 | 中建七局建筑装饰工程有限公司 | A kind of super-hydrophobic acrylic coating of antistatic, preparation method and applications |
| CN111777936A (en)* | 2020-07-03 | 2020-10-16 | 江苏新光镭射包装材料股份有限公司 | Scratch-resistant fingerprint-resistant touch decorative film and preparation process thereof |
| CN112143322A (en)* | 2020-09-04 | 2020-12-29 | 浙江玖龙新材料有限公司 | Formula and preparation method of high-self-leveling acrylic emulsion |
| CN113416459A (en)* | 2021-06-11 | 2021-09-21 | 安徽强邦新材料股份有限公司 | Printing plate protective coating and preparation method thereof |
| CN113416459B (en)* | 2021-06-11 | 2022-04-19 | 安徽强邦新材料股份有限公司 | Printing plate protective coating and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
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