有机硅/SiO_2杂化溶胶改性丙烯酸树脂及性能研究
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摘要
以丙烯酸(AA)、丙烯酸丁酯(BA)、丙烯酸羟乙酯(HEA)、甲基丙烯酸甲酯(MMA)、正硅酸乙酯(TEOS),γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)、甲基三乙氧基硅烷(MTES)和二苯基二甲氧基硅烷(DDS)为原料,采用溶液聚合法合成有机硅/SiO_2杂化溶胶改性丙烯酸树脂。探讨不同种类有机硅/SiO_2杂化溶胶及含量对树脂性能的影响。通过红外光谱表征了溶胶及固化后杂化涂层的结构,并测试了漆膜的物理性能以及通过电化学阻抗和浸泡实验对涂膜耐蚀性进行分析。结果表明:有机硅/SiO_2杂化溶胶成功地接枝到水性丙烯酸树脂上。当有机硅/SiO_2杂化溶胶添加量为10%(质量分数)时,杂化涂层具有良好的柔韧性和附着力,涂膜硬度6H,光泽度104,漆膜长期稳定,具有优异的耐蚀性。
Organosilicon/SiO_2 hybrid sols modified water borne acrylic resins were synthesized via solution polymerization process with acrylic-acid(AA), butyl-acrylate(BA), hydroxyethyl-acrylate(HEA),methyl-methacrylate(MMA), tetraethyl(TEOS), 3-methacryloxypropyltrimethoxysilane(KH-570), methyltriethoxysilane(MTES) and diphenyl dimethoxy silane as raw material. The effect of different amount and specie of organosilicon/SiO_2 hybrid sols on the properties of the resin was investigated. The structure of the prepared sols and resin films were characterized by infrared spectroscopy(FT-IR). The corrosion resistance and mechanical properties of the coatings on tinplate were as examined by means of immersion test, electrochemical impedance spectroscopy(EIS) and relevant mechanical testing means. The results showed that the organosilicon/SiO_2 hybrid sol could be successfully grafted onto the acrylic molecules.Among others, the hybrid resin coating with 10%(mass fraction) organosilicon/SiO_2 hybrid sol exhibited excellent comprehensive performance: such as excellent flexibility and adhesion; hardness and gloss as high as 6H and 104, respectively, while high corrosion resistance and long term stability etc.
Organosilicon/SiO_2 hybrid sols modified water borne acrylic resins were synthesized via solution polymerization process with acrylic-acid(AA), butyl-acrylate(BA), hydroxyethyl-acrylate(HEA),methyl-methacrylate(MMA), tetraethyl(TEOS), 3-methacryloxypropyltrimethoxysilane(KH-570), methyltriethoxysilane(MTES) and diphenyl dimethoxy silane as raw material. The effect of different amount and specie of organosilicon/SiO_2 hybrid sols on the properties of the resin was investigated. The structure of the prepared sols and resin films were characterized by infrared spectroscopy(FT-IR). The corrosion resistance and mechanical properties of the coatings on tinplate were as examined by means of immersion test, electrochemical impedance spectroscopy(EIS) and relevant mechanical testing means. The results showed that the organosilicon/SiO_2 hybrid sol could be successfully grafted onto the acrylic molecules.Among others, the hybrid resin coating with 10%(mass fraction) organosilicon/SiO_2 hybrid sol exhibited excellent comprehensive performance: such as excellent flexibility and adhesion; hardness and gloss as high as 6H and 104, respectively, while high corrosion resistance and long term stability etc.
引文
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[13] Liu G M, Yang X D, Lin J Y, et al. Influence of MTES content on the properties of Al2O3/organosilicone/SiO2hybrid coatings[J].Chin. J. Mater. Res., 2012, 26:402(刘光明,杨晓东,林继月等. MTES含量对Al2O3/有机硅/SiO2杂化涂层性能的影响[J].材料研究学报, 2012, 26:402)
[14] Lin J Y, Liu G M, Chen G. Influence of DDS content on the prop‐erties of organosilicon/SiO2hybrid coatings[J]. J. Chin. Soc. Cor‐ros. Prot., 2011, 31:116(林继月,刘光明,陈刚. DDS含量对有机硅/SiO2杂化涂层性能的影响[J].中国腐蚀与防护学报, 2011, 31:116)
[15] Kozakiewicz J, Ofat I, Trzaskowska J. Silicone-containing aque‐ous polymer dispersions with hybrid particle structure[J]. Adv.Colloid Interface Sci., 2015, 223:1
[2] Goodarzi I M, Farzam M, Shishesaz M R, et al. Eco-friendly, acryl‐ic resin-modified potassium silicate as water-based vehicle for anti‐corrosive zinc-rich primers[J]. J. Appl. Polym. Sci., 2014, 131:40370
[3] Pilch-Pitera B, Kozakiewicz J, Ofat I, et al. Silicone-acrylic hybrid aqueous dispersions of core-shell particle structure and correspond‐ing silicone-acrylic nanopowders designed for modification of pow‐der coatings and plastics. Part III:Effect of modification with select‐ed silicone-acrylic nanopowders on properties of polyurethane pow‐der coatings[J]. Prog. Org. Coat., 2015, 78:429
[4] Yuan Y, Chen N, Liu R, et al. A novel acrylic prepolymer/methacry‐late modified nano-SiO2composite used for negative photoresist[J]. Mater. Res. Bull., 2014, 50:392
[5] Jang D E, Lee J Y, Jang H S, et al. Color stability, water sorption and cytotoxicity of thermoplastic acrylic resin for non metal clasp denture[J]. J. Adv. Prosthodont., 2015, 7:278
[6] Li K Z, Guo Q, Zhang L L, et al. Synthesis and characterization of Si-substituted hydroxyapatite bioactive coating for SiC-coated car‐bon/carbon composites[J]. Ceram. Int., 2017, 43:1410
[7] Hamdy A S, Butt D P. Environmentally compliant silica conversion coatings prepared by sol-gel method for aluminum alloys[J]. Surf.Coat. Technol., 2006, 201:401
[8] Easton T, Poultney S. Waterborne silicone-organic hybrid coatings for exterior applications[J]. J. Coat. Technol. Res., 2007, 4:187
[9] Martínez-Zapata O, Méndez-Vivar J, Bosch P, et al. Synthesis and characterization of amorphous aluminosilicates prepared by sol-gel to encapsulate organic dyes[J]. J. Non-Cryst. Solids, 2011, 357:3480
[10] Zhang J H, Chen Y S. Studies on application of sol-gel method[J].Guangdong Chem. Ind., 2008, 35(3):47(张健泓,陈优生.溶胶-凝胶法的应用研究[J].广东化工, 2008,35(3):47)
[11] Ma L, Wang G J, Dai J F. Preparation and properties of reduced graphene oxide/polyimide composites produced by in-situ polym‐erization and solution blending methods[J]. New Carbon Mater.,2016, 31:129(马朗,王国建,戴进峰.原位聚合法与溶液混合法制备石墨烯/聚酰亚胺复合材料及其性能[J].新型碳材料, 2016, 31:129)
[12] Chen G, Liu G M, Yao J, et al. Study on the electrochemical im‐pedance spectroscopy of silicone/SiO2hybrid coating[J]. Surf.Technol., 2008, 37(6):47(陈刚,刘光明,姚敬等.有机硅/SiO2杂化涂层电化学阻抗研究[J].表面技术, 2008, 37(6):47)
[13] Liu G M, Yang X D, Lin J Y, et al. Influence of MTES content on the properties of Al2O3/organosilicone/SiO2hybrid coatings[J].Chin. J. Mater. Res., 2012, 26:402(刘光明,杨晓东,林继月等. MTES含量对Al2O3/有机硅/SiO2杂化涂层性能的影响[J].材料研究学报, 2012, 26:402)
[14] Lin J Y, Liu G M, Chen G. Influence of DDS content on the prop‐erties of organosilicon/SiO2hybrid coatings[J]. J. Chin. Soc. Cor‐ros. Prot., 2011, 31:116(林继月,刘光明,陈刚. DDS含量对有机硅/SiO2杂化涂层性能的影响[J].中国腐蚀与防护学报, 2011, 31:116)
[15] Kozakiewicz J, Ofat I, Trzaskowska J. Silicone-containing aque‐ous polymer dispersions with hybrid particle structure[J]. Adv.Colloid Interface Sci., 2015, 223:1