耐高温防腐蚀涂料的研制
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摘要
论文综述了耐温防腐涂料的发展概况和涂装系统，详细地研究了富锌底漆中正硅酸乙酯水解的动力学过程和偶联剂的作用机理及有机硅树脂、无机骨料对金属基耐温防腐涂层的影响。
正硅酸乙酯的水解过程中研究了水解反应的动力学方程及温度、正硅酸乙酯浓度、催化剂浓度对水解反应的影响，同时对干凝胶的性能运用差热、红外光谱、X射线光谱进行了分析，从而确定了正硅酸乙酯水解的最佳工艺条件：在70℃，PH=1～2时，在一定的时间内向醋酸丁酯、乙二醇丁醚、正丁醇的混合液中以1～2滴／秒的速度滴加正硅酸乙酯。这时的水解液清澈透明，保存时间可达4个月之久。
制备金属基耐温防腐涂层的过程中分别研究了偶联剂的加入、涂层厚度、骨料的选择对涂层性能的影响以及底部涂层中锌粉浆的保存和制备。研究得出：当涂刷三层涂层且涂层厚度达到105～110μm时，具有良好的耐温防腐性能；选择鳞片状云母氧化铁和无机陶瓷原料作为中间涂层和表面涂层的骨科能有效防止腐蚀介质的侵蚀并能提高涂层的耐温性能。在涂刷涂料之前，将602型偶联剂配制成2％的醇溶液直接涂覆于基材上可改善涂层的附着力、耐温性及耐腐蚀性能。制备的金属基高温防腐涂层具有抗热震性好和长期耐温高达700℃的性能，并且可抵抗各种化学品的侵蚀。此外，还研究了涂层防腐蚀机理。分析指出：由于砖树脂具有R—Si—O—Si—R这样一个特殊的结构，使它既具有无机物又具有有机物的性质。随着温度的升高，Si—OH之间的缔合更加完全，使涂层得到充分固化，是涂膜具有耐高温防腐优异性能的关键。
In this paper , the development of heat resistant and anticorrosive coating was briefly reviewed .Tetraethylorthesilicate(TEOS) oligomers were prepared through the hydrolysis and condensation of TEOS with water, the author aslo explained how siloxane and inorganic pigments had effects on th properties of coating.
Served as bond in base coating, hydrolysism, condensation and kinetic behavior of TEOS were studied. The mixture of TEOS oligomers was characterized by FTIR DTA and XRD.The data showed that ceramic coating properties were affected by temperature TEOS and analyst concentration. The best way to hydrolyze TEOS was decided that under the condition of 70 and pH=l-2, dripping TEOS into the mixture of n-butyl alcohol n-butyle acetate and ethylene glycol monobutyl ether, the production could be preserved more than four months ,and the solution is lucid.
Analysis of these results obtained by the process of coating reveals that interesting correlation is found in conjuction with the coupling agent, the thickness of coating, pigments and the properties of coating: (i) it concluded that the coating consisted of base coat intermediated coat and top coat, especially when the total thickness is 105-110 u m, it provided the coating with the best properties to resist heat and corrosion.(ii) because of its scalelike structure MIO which was worked as the pigments in the intermediate coat could increase the properties of heat-resistance and protect metal from corrosive media effectively.(iii)Before varnishing, substrate had to be treated with coupling agent 602 which was diluted to 2% in ethanol solution .It was found that the metal treated in this way could promoted ashesion of coating. In addition, (iiii) studies of the anti-corrosion mechanism companing the molecular structure of silicone resins and natural guartz, the resin can be considered as organically modified
quartz. Unlike quartz, however , every fourth oxygen group of a silicone resin is replaced by an organic group R, such as R-Si -O-Si-R.Chemically, silicone resins lie between purely inorganic and purely organic componds. When temperature rised, two silane molecular incorporate added water (H2O) and release two molecular of alcohol, as a result, coating was cured entiredly. The cured coating has high ability to resist heat and corrosion.
正硅酸乙酯的水解过程中研究了水解反应的动力学方程及温度、正硅酸乙酯浓度、催化剂浓度对水解反应的影响，同时对干凝胶的性能运用差热、红外光谱、X射线光谱进行了分析，从而确定了正硅酸乙酯水解的最佳工艺条件：在70℃，PH=1～2时，在一定的时间内向醋酸丁酯、乙二醇丁醚、正丁醇的混合液中以1～2滴／秒的速度滴加正硅酸乙酯。这时的水解液清澈透明，保存时间可达4个月之久。
制备金属基耐温防腐涂层的过程中分别研究了偶联剂的加入、涂层厚度、骨料的选择对涂层性能的影响以及底部涂层中锌粉浆的保存和制备。研究得出：当涂刷三层涂层且涂层厚度达到105～110μm时，具有良好的耐温防腐性能；选择鳞片状云母氧化铁和无机陶瓷原料作为中间涂层和表面涂层的骨科能有效防止腐蚀介质的侵蚀并能提高涂层的耐温性能。在涂刷涂料之前，将602型偶联剂配制成2％的醇溶液直接涂覆于基材上可改善涂层的附着力、耐温性及耐腐蚀性能。制备的金属基高温防腐涂层具有抗热震性好和长期耐温高达700℃的性能，并且可抵抗各种化学品的侵蚀。此外，还研究了涂层防腐蚀机理。分析指出：由于砖树脂具有R—Si—O—Si—R这样一个特殊的结构，使它既具有无机物又具有有机物的性质。随着温度的升高，Si—OH之间的缔合更加完全，使涂层得到充分固化，是涂膜具有耐高温防腐优异性能的关键。
In this paper , the development of heat resistant and anticorrosive coating was briefly reviewed .Tetraethylorthesilicate(TEOS) oligomers were prepared through the hydrolysis and condensation of TEOS with water, the author aslo explained how siloxane and inorganic pigments had effects on th properties of coating.
Served as bond in base coating, hydrolysism, condensation and kinetic behavior of TEOS were studied. The mixture of TEOS oligomers was characterized by FTIR DTA and XRD.The data showed that ceramic coating properties were affected by temperature TEOS and analyst concentration. The best way to hydrolyze TEOS was decided that under the condition of 70 and pH=l-2, dripping TEOS into the mixture of n-butyl alcohol n-butyle acetate and ethylene glycol monobutyl ether, the production could be preserved more than four months ,and the solution is lucid.
Analysis of these results obtained by the process of coating reveals that interesting correlation is found in conjuction with the coupling agent, the thickness of coating, pigments and the properties of coating: (i) it concluded that the coating consisted of base coat intermediated coat and top coat, especially when the total thickness is 105-110 u m, it provided the coating with the best properties to resist heat and corrosion.(ii) because of its scalelike structure MIO which was worked as the pigments in the intermediate coat could increase the properties of heat-resistance and protect metal from corrosive media effectively.(iii)Before varnishing, substrate had to be treated with coupling agent 602 which was diluted to 2% in ethanol solution .It was found that the metal treated in this way could promoted ashesion of coating. In addition, (iiii) studies of the anti-corrosion mechanism companing the molecular structure of silicone resins and natural guartz, the resin can be considered as organically modified
quartz. Unlike quartz, however , every fourth oxygen group of a silicone resin is replaced by an organic group R, such as R-Si -O-Si-R.Chemically, silicone resins lie between purely inorganic and purely organic componds. When temperature rised, two silane molecular incorporate added water (H2O) and release two molecular of alcohol, as a result, coating was cured entiredly. The cured coating has high ability to resist heat and corrosion.
引文
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[3] 刘登良，重防腐涂料及其在工程中的应用(Ⅱ)，现代涂料与涂装，1990(1)：2～4
[4] 田中利，一种特殊涂料，日本专利公开昭61-57609
[5] 陈爱群，有机氟工业，1992(2)：1～14
[6] 敬松，涂料用含氟聚合物，化工新型材料，1994(1)：25～27，22
[7] 倪玉德，含氟聚合物及含氟涂料Ⅰ，涂料工业，2000(4)：29～30
[8] 童身毅，环氧改性氟树脂研究，涂料工业，1998(2)：3～4
[9] Sagawa; Chiaki ,Katagiri; Manabu,Kurashina; Tom ,Thermosetting powder coating material, US5356971,1993
[10] K．A 波利亚科夫，非金属化学耐腐蚀材料(第三版)，354页
[11] 吴森纪，龚守贤，有机硅及其应用(第三版)，科学技术文献出版社，213页
[12] 幸松民，王一路，有机硅合成工艺及产品应用(第三版)，化学工业出版社，743页
[13] 免田化学工业，工业材料(日)，1979(6)：8
[14] plane coating, Morder Paint and Coating,1978(10):131～132
[15] 同[11]，230页
[16] GB112396 (1968)
[17] Fets cher ,CA.etdl. De2308201,1973
[18] 万敏，耐高温涂料，涂料工业，1990(5)：591
[19] 鲁照玲，刘光明，周宇，环氧改性氟树脂研究，涂料工业，1999，29(4)：1～2
[20] 伊藤邦雄，日本：日刊工业新闻社，1990．4921
[21] 刘珑，郑庆慧，张留成等，高分子材料科学与工程，1990(6)：30～36
[22] 刘俊峰，有机硅/聚氨酯改性树脂的研制，化工新型材料，1998，26(4)：26
[23] Chi; Frank K.,Phenolic resin-containing aqueous compositions,US4584340,1984
[24] 高学敏等，粘接和粘接技术手册(第二版)，四川科学技术出版社，413页
[25] 邬润德，童筱莉，周安定，有机硅氧烷原位、接枝聚合改性丙烯酸树脂研究，涂料工业，1999(5)：5～8
[26] Kusami A etal ,Curable composition,Ep627472,1994
[27] Masuoka. S. etal ,Antifouling paint,Ep297505,1989
[28] Obota k.etal.Jp-kokai, 平 5-230403,1993
[29] Tolentino L.A., Acrylic-functional silicone resin compositions US4568566(1986)
[30] 同[24]，426页
[31] 同[1]，91页
[32] Schutt; John B.,Silicate binders and coatings ,US4479824(1983)
[33] 刘登峰，水玻璃的改性，特种涂料，1973(1)：42～43
[34] 特开日召52-53000
[35] NASN-TN-D-106(美国宇航局特刊)
[36] GB1258405
[37] 特公昭51-2331
[38] 葛嵘，有机硅树脂涂料，涂料工业，1981(1)：7
[39] 同[24]433页
[40] 孔繁芬，唐裕华，高温漆的研究，表面技术，1992(21)：116～119
[41] 席时俊，富锌底漆评介，中国涂料，2000(2)：23～25
[42] 金晓鸿，郑添水，鳞片状锌基环氧富锌底漆的研究，材料保护，1999(32)：25-26
[43] G.A salensky,Modified zinc-rich coatings ,US4370382. 1983
[44] R.Romagnoli, B .delam,etal, Suface Coatings, 1998(20):200～203
[45] l.Veleva, J chin, progress in organic coatings, 1999(36):211～216
[46] Process and arrangement for contacting of metallic pads disposed on substrate foils,German Patent No 2,557,401(1976)
[47] 同[2]，52页
[48] 郭晓军，水溶性硅酸锂富锌涂料的研制，腐蚀与防护，2000(21)：274～275
[49] 季瑞峰，钱叶苗，刘登良，水性无机富锌涂料，涂料工业，1999(9)：7～10
[50] 战凤昌，李悦良，专用涂料，化学工业出版社，1996，139页
[51] 和田保，制造方法，特开昭54-34332
[52] 崛井清之，村田逞诠，特种涂料，特公昭53-140322
[53] 加藤康，防腐蚀涂料的配方，特公昭54-39439
[54] 白井健三，涂装涂料(日)，1979(8)：31
[55] 深山美代治，大西正之，室温硬化后涂装可能的组成物，特公昭54-36929
[56] 伊藤，邦雄，硬化物组成，特公昭57-59270
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