活性硅醇基聚氨酯水分散体的合成及其防腐性能
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摘要
水玻璃作为一种廉价的矿物质,经提纯可得到活性硅醇,以其作为内交联剂可应用于聚氨酯的合成中。对不同活性硅醇添加量合成的聚氨酯水分散体粒径及其涂膜的吸水率、接触角、动电位极化曲线、热重和扫描电镜作了测试分析,结果表明当活性硅醇添加量为30%时,水分散体平均粒径最小,为28.83nm;随着活性硅醇添加量的增加,涂膜吸水率增大,接触角反而减小;动电位极化曲线拟合结果表明,当活性硅醇添加量为70%时,涂膜腐蚀电流密度最小且极化电阻最大;红外光谱和扫描电镜分别可以确定水分散体结构中含有Si—O—Si、Si—O—C的基团以及涂膜中含有二氧化硅粒子,说明活性硅醇在体系中不仅参与主链反应,还以无机粒子的形态存在于其中;热重分析表明活性硅醇的引入显著提高了涂膜的热稳定性。
Active silanol can be obtained from water glass by purification and be used as an internal crosslinking agent in the synthesis of polyurethane. Polyurethane aqueous dispersions with different amount of active silanol were investigated and analyzed by measuring their particle size,water absorption rate,contact angle,potentiodynamic polarization curves,thermogravimetry and scanning electron microscopy. The results showed that average particle size of the water dispersion reached the minimum of 28.83 nm,when the amount of active silanol was 30%. With the increase of the amount of active silanol,the water absorption rate of the coating increased,but the contact angle decreased. And the potentiodynamic polarization curves showed that when the amount of active silanol was 70%,the corrosion current density of the coating was the lowest and the polarization resistance was the highest. Infrared spectroscopy and scanning electron microscopy can respectively determine that structure of the dispersions contained Si—O—Si and Si—O—C groups and the coating contained silica particles,which indicated that active silanol took part in the chain reaction in the state of inorganic particles. Besides,thermogravimetric analysis demonstrated that the introduction of active silanol significantly improved the thermal stability of the coating.
Active silanol can be obtained from water glass by purification and be used as an internal crosslinking agent in the synthesis of polyurethane. Polyurethane aqueous dispersions with different amount of active silanol were investigated and analyzed by measuring their particle size,water absorption rate,contact angle,potentiodynamic polarization curves,thermogravimetry and scanning electron microscopy. The results showed that average particle size of the water dispersion reached the minimum of 28.83 nm,when the amount of active silanol was 30%. With the increase of the amount of active silanol,the water absorption rate of the coating increased,but the contact angle decreased. And the potentiodynamic polarization curves showed that when the amount of active silanol was 70%,the corrosion current density of the coating was the lowest and the polarization resistance was the highest. Infrared spectroscopy and scanning electron microscopy can respectively determine that structure of the dispersions contained Si—O—Si and Si—O—C groups and the coating contained silica particles,which indicated that active silanol took part in the chain reaction in the state of inorganic particles. Besides,thermogravimetric analysis demonstrated that the introduction of active silanol significantly improved the thermal stability of the coating.
引文
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[2]AKINDOYO J O,BEG M D H,GHAZALI S,et al.Polyurethane types,synthesis and applications-a review[J].RSC Advances,2016,6(115):114453-114482.
[3]袁天梦,张博晓,田军,等.水性聚氨酯防腐涂料的研究现状[J].现代涂料与涂装,2017,20(2):31-34,37.YUAN T M,ZHANG B X,TIAN J,et al.Research status on waterborne ployurethane anti-corrosive coatings[J].Modern Paint&Finishing,2017,20(2):31-34,37.
[4]WU G,KONG Z,CHEN C,et al.Crosslinking reaction and properties of two-component waterborne polyurethane from terpene-maleic ester type epoxy resin[J].Journal of Applied Polymer Science,2013,128(1):132-138.
[5]潘红霞,肖明宇,陈大俊.聚氨酯/丙烯酸酯复合乳液的制备方法及性能研究进展[J].化工进展,2006,25(9):1064-1068.PAN H X,XIAO M Y,CHEN D J.Preparation and properties of polyurethane/polyacrylate(PUA)hybrid emulsion[J].Chemical Industry and Engineering Progress,2006,25(9):1064-1068.
[6]颜财彬,傅和青.水性聚氨酯的改性研究进展[J].化工进展,2011,30(12):2658-2664.YAN C B,FU H Q.Research progress of modification technology for waterborne polyurethane[J].Chemical Industry and Engineering Progress,2011,30(12):2658-2664.
[7]CHATTOPADHYAY D K,RAJU K V S N.Structural engineering of polyurethane coatings for high performance applications[J].Progress in Polymer Science,2007,32(3):352-418.
[8]王寅,傅和青,颜财彬,等.纳米材料改性水性聚氨酯研究进展[J].化工进展,2015,34(2):463-469.WANG Y,FU H Q,YAN C B,et al.Research progress of waterborne polyurethane modified by nanomaterials[J].Chemical Industry and Engineering Progress,2015,34(2):463-469.
[9]戴俊,陈焕懿,韦凌志.聚氨酯/无机纳米复合材料研究进展[J].化工进展,2014,33(9):2380-2386.DAI J,CHEN H Y,WEI L Z.Research progress in polyurethane/inorganic nanomaterial composites[J].Chemical Industry and Engineering Progress,2014,33(9):2380-2386.
[10]刘玄,杨政鹏,管学茂,等.聚醚基聚氨酯/水玻璃凝胶的制备及性能[J].化工新型材料,2015(7):224-226.LIU X,YANG Z P,GUAN X M,et al.Preparation and property of the polyurethane/silicate gel based on polymer glycol[J].New Chemical Materials,2015(7):224-226.
[11]ABE Y,SUGIMOTO N,NAGAO Y,et al.Preparation of a gel-like silica glass by the condensation of silicic acid in organic solvents[J].Yogyo-Kyokai-Shi,1987,7(95):672-675.
[12]黄光福.多苯基多次甲基多异氰酸酯中—NCO基含量的测定[J].广州化工,1989(2):61-62.HUANG G F.Determination of—NCO group content in polymethylene polyphenyl polyisocyanate[J].Guangzhou Chemical Industry,1989(2):61-62.
[13]石健,王东升,杭喻文.不同条件对活性硅酸聚合的影响[C]//中国环境科学学会.2014中国环境科学学会学术年会.四川成都:中国环境科学出版社,2014:4610-4615.SHI J,WANG D S,HANG Y W.Effect on polymerization of active silicic acid in different conditions[C]//Chinese Society For Environmental Science.Annual Meeting of Chinese Society for Environmental Science in 2014.Chengdu,Sichuan,China Environmental Science Press,2014:4610-4615.
[14]TOMACHUK C R,ELSNER C I,DI SARLI A R.Corrosion resistance of steel/zinc with silicate nanoparticles/polyurethane paint systems in Na Cl solution[J].Journal of Materials Science and Engineering A,2012,11(2):693-711.