硅烷在涂料中的应用 silanes for coatings

Silanes for Coatings硅烷在涂料中的应用,Shiu-Chin Cindy Su蘇黃秀琴Momentive Performance MaterialsShiu-Chin.S914-784-4905,Company History 公司的历史,1993 Divestiture,2000 Name Change,2003 Acquisition,Late 1950s,2006 Divestiture,Function of Silanes in Coatings硅烷在涂料中的特殊功能,Adhesion Promotion 增强附着力Especially between organic polymers and inorganic oxide substrates 特别是在有机聚合物与无机氧化物之间Some examples exist for adhesion to nonfunctional organic substrates 在难附着的有机底材上增强附着力Crosslinking 交联剂Convert reactive polymers (isocyanate, polyol, polyamine) to moisture cure chemistry 可反应性聚合物具有潮气固化反应的特点VOC Reduction 减少 VOCDispersion 帮助分散Compatibilize high-energy particulates with organic matrices 帮助高能量粒子在有机物中的分散；,Silanes are Dual-Functional Molecules硅烷是双功能的分子,Organic portion bonds or interacts with a polymer or organic surface. 有机基团可以与聚合物或有机表面形成化学键；Silane portion bonds or interacts with metal, glass or inorganic surface (adhesion). 硅烷基团可以与金属，玻璃等无机表面形成化学键；Can react with other silane-modified polymers (crosslinking). 可与其它硅烷改性的聚合物反应（交联）,Hydrolysis and Condensation水解和缩合反应,1. Hydrolysis Reaction 水解反应,OH,H,2,N(CH,2,),3,Si (OCH,3,),3,H,2,N(CH,2,),3,Si OH + 3 CH,3,OH,(,Silquest,A-1110,silane,),OH,2. Condensation 缩合反应,OH,OH,H,2,N(CH,2,),3,Si OH + HO,Si,H,2,N(CH,2,),3,Si,O,Si,OH,OH,H,2,O,- H,2,O,Surface,silanol,Functionalized,surface,Hydrolysis and Condensation of Organofunctional Silanes pH值对硅烷水解和缩合反应的影响,log k,pH,水解(kobs, s-1),缩合(kobs, M-1s-1),E. R. Pohl et. al.,Function of Silanes in Coatings硅烷在涂料中的特殊功能,Adhesion Promotion 增强附着力Especially between organic polymers and inorganic oxide substrates 特别是在有机聚合物与无机氧化物之间Some examples exist for adhesion to nonfunctional organic substrates 在难附着的有机底材上增强附着力Crosslinking 交联剂Convert reactive polymers (isocyanate, polyol, polyamine) to moisture cure chemistry 可反应性聚合物具有潮气固化反应的特点VOC Reduction 减少 VOCDispersion 帮助分散Compatibilize high-energy particulates with organic matrices 帮助高能量粒子在有机物中的分散；,How Does Silane Enhance Adhesion硅烷增加附着力的化学原理,Metal = Substrate,Match FG with Resin system有机基团与树脂的反应性相匹配,FG = 有机基团,Relative Silane Effectiveness有机硅烷对无机材料的反应性,Silica, Quartz, Glass 石英，玻璃Aluminum, Alumina 铝材，氧化铝Copper 铜Wollastonite 硅酸盐Aluminosilicates (clays)硅酸铝Mica云母Talc 滑石粉Iron, steel 铁，钢Asbestos 石棉Nickel 镍Zinc 锌Lead 铅Calcium carbonate (chalk)碳酸钙Calcium sulfate (gypsum)硫酸钙Barium sulfate (baryte)硫酸钡Carbon black (untreated)碳黑Graphite 石墨,Excellent优异Good好Some一般None无作用,How do you use a Silane? 如何使用硅烷,Two ways 两种方法 ： Primer 作为底涂 Integral Blend 添加在涂料中,Primer: Pretreat substrate with silane. Very efficient use of silane for adhesion promotion, not efficient resin crosslinking (minimal stability problem), two step process.底涂:硅烷对基材预处理，对附着力促进非常有效，不影响树脂的贮存稳定性，两步法底涂涂料。Integral blend: Mix silane into coating formulation. Much better for crosslinking, also good for adhesion promotion. Possible silane hydrolysis and condensation on storage. Most customers will do it this way.将硅烷添加到涂料配方中，增加树脂体系的交联密度，同时促进附着力。在储存时，硅烷可能会发生水解和缩合反应，影响储存稳定性。,Typical Primer Formulation硅烷底涂的参考配方,Primer suitable for an epoxy or urethane system适用于环氧或聚氨酯涂料：组份重量份Silquest A-1100或A-1120硅烷 5SDA-30 醇(91.11%乙醇+8.89%甲醇) 40蒸馏水 Distilled water 5甲苯 toluene 40n-丁醇 n-Butanol 5丁基纤维素Butyl Cellosolve 5,Application of Primer 底涂的应用,Dissolve 0.5-5.0 weight percent silane in a compatible, volatile solvent (or mixture) 溶解0.5-5.0硅烷于挥发溶剂中Alcohols are most commonly used, for water compatibility.对不溶于水的硅烷，通常使用乙醇，以保持与水的相溶性Equal parts water (based on silane) may be added to prehydrolyze silane if water is compatible with the solvent. 加入与硅烷相同量的水来预水解If primer is to be used immediately, the solution may be acidified.如果底涂马上使用，溶液可以是酸性的Apply to clean, grease-free surface. 涂布于清洁无油的表面Wiping, spraying, brushing, dipping，擦涂，喷涂，刷涂，浸涂Film thickness 0.1 mil ， 膜厚70 days at RT - 70 days at 50CApplication conditions 应用条件 120 microns dry deposit on Lenetta black card 28days RTTest method 测试方法 Wet Scrub test DIN 53778,Impact of ageing of CoatOSil* 193 on Wet Scrub of VeoVa based paints CoatOSil VX193对VeoVa乳液涂料耐湿擦洗性的影响,Conclusion;结论CoatOSil VX-193 Improves Wet Scrub resistances.Ageing of the latex in normal or accelerated conditions have less impact on CoatOSil VX-193CoatOSil VX-193 提高耐湿擦洗性。 CoatOSil VX-193在正常或加速条件下熟化， 对耐擦洗性的影响变化不大。,FEATURES 特色,BENEFITS 优点,Water stable silane composition use full for emulsion polymerization水稳定型硅烷用于乳液聚合中Good hydrolytic Stability 水解稳定性Lower solvent content 低溶剂含量Organic & inorganic functionality 同时具有有机和无机的功能,Low VOC generation upon cure 在固化时，产生低VOCBetter control of polymerization 较好地控制聚合反应Very good Wet Scrub resistance 提高耐擦洗性Enhanced hydrophobicity 增强憎水性Higher polymer stability upon ageing在乳液熟化期，聚合物具有高稳定性；Room temperature self-crosslinking 室温自交联,Features and Benefits of CoatOSil* VX-193CoatOSil VX193 的特色和优点,Use of Silanes to Cross-link Coatings硅烷作为涂料的交联剂,Two Systems: Solvent Borne and Water Borne 两种系统 : 溶剂型和水性Two main ways: 两种主要路经:Co-polymerize共聚合Use a functional silane as a monomer in polymer formation 选用具有反应活性的硅烷作为单体形成聚合物Post-Addition/Blend 后添加/混合After the polymer is formed, react a functional silane with it. 形成聚合物后，再与反应活性的硅烷反应,Functionalizing Anionic Resin with Epoxy Silanes阴离子树脂与环氧硅烷的反应,*Silquest is a trademark of Momentive Performance Materials Inc.,Epoxysilanes for Integral blend modification of WB systems 应用于水性涂料的环氧硅烷,1K,2K,Silquest A-1871,CoatOSil* 2287,Silquest A-187,CoatOSil* 1770,Wood Coating Formulation 木器漆配方,Component characteristics 组成Joncryl 537 : Acrylic emulsion 丙烯酸乳液 (Johnson Polymer ) Solid: 46.5% 固含: 46.5% Acid Number: 51 酸值: 51 Tg: 50cJonwax 35 : Polyethylene wax emulsion 聚乙烯腊乳液 (Johnson Polymer )PE-PUD: Polyether polyurethane 聚醚型聚氨酯 (Laboratory product) Solid: 24% 固含: 24% NMP: 4% Acid Number: 30 酸值: 30CoatOSil* 2287: gamma-glycidoxypropyl methyldiethoxysilane (Momentive Performance Materials)CoatOSil 1211: Non-foaming wetting agent 无泡润湿剂 (Momentive Performance Materials)Dowanol DPnB 二丙二醇丁醚 (Dow)：Coalescent,glycidoxypropylmethyl-diethoxysilane,CoatOSil* 2287,3-缩水甘油醚基丙基甲基二乙氧基硅烷,Wood Coating Formulation 木器漆配方,Formulation characteristics:pHViscosity 黏度Solid 固含Binder ratio (Acrylic/PUD)% epoxysilanes 环氧硅烷/mgKOH/g,Wood Coating Application,Viscosity黏度 20s DIN4Application 施工工艺 Spray 喷涂Dry deposit 涂布量 130-170g/m ( total ) Two layers 两道Panel 板材 Oak veneered board橡木板 Sanding between each layerDrying time 干燥时间 40C 1 hour 28 days at room temperature 40C 1小时室温放置28 天,0,1,2,3,4,5,Ammonia 氨水(10%) - 2min,Black tea 红茶 - 24h,Actone 丙酮 - 2min,Ethyl-Butyl acetate乙酸乙酯/丁酯 - 2min,Ethyl alcohol乙醇 (48%) 60min,0,1,2,3,4,5,Acetic acid 乙酸 (44%) - 60min,Ammonia 氨水(10%) - 2min,Black tea 红茶 - 24h,Acetone 丙酮 - 2min,Ethyl-Butyl acetate 乙酸乙酯/乙酸丁酯 - 2min,Ethyl alcohol乙醇 (48%) 60min,ISO 4211-19790: severe effect; 5: no effect 0: 严重影响; 5: 无影响,Standard 参考配方,X-Linked 测试配方,0.08% epoxysilanes/ mgKOH/g,+1.2% CoatOSil* 2287,Impact of CoatOSil* 2287 onStaining & Chemical Resistance ISO 4211 (1979) CoatOSil* 2287 对耐污&耐化学性的影响,Acetic acid 乙酸 (44%) - 60min,0,1,2,3,4,5,Acetic acid 乙酸 - 60min,Ammonia 氨水(10%) - 2min,Black tea 红茶 - 16h,Acetone 丙酮 - 10s,Ethyl-Butyl Acetate 乙酸乙酯/丁酯 - 10s,Ethyl alcohol 乙醇 (48%)- 60min,0,1,2,3,4,5,Acetic acid 乙酸 - 60min,Ammonia 氨水(10%) - 2min,Black tea 红茶 - 16h,Acetone 丙酮 - 10s,Ethyl-Butyl Acetate乙酸乙酯/丁酯 - 10s,Ethyl alcohol乙醇 (48%)- 60min,DIN 68861-1B0: severe effect; 5: no effect 0: 严重影响; 5: 无影响,Standard 参考配方,X-Linked 测试配方,+1.2% CoatOSil* 2287,0.08% 环氧硅烷 / mgKOH/g,Impact of CoatOSil* 2287 onStaining & Chemical Resistance DIN 68861 1B CoatOSil* 2287 对耐污&耐化学性的影响,+1.2% CoatOSil* 2287,Impact of CoatOSil* 2287 onStaining & Chemical Resistance DIN 68861 1A CoatOSil*