氟碳纳米复合环保涂料的研究
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摘要
本文研究了一种环保型含氟纳米复合涂料，可用于高性能外墙涂料。本研究包括以下三方面的内容。
第一是纳米颜料的制备。使用溶胶一凝胶法以钛酸丁酯为原料制备了纳米TiO_2粉末。实验结果表明水解体系的PH值在2.5左右时纳米TiO_2的产率最高，透射电镜测试表明产品粒径在50～100nm之间，X衍射测试表明产品晶型为金红石型。为了使纳米TiO_2粉末达到作为涂料颜料的要求，对其进行了改性。使用三种改性方法对纳米粒子改性，改性产品的活化指数和接触角测试结果均表明亲油性改性的效果：钛酸酯偶联剂改性＞硅烷偶联剂改性＞类酯化改性。
第二是含氟聚合物乳液的合成。使用甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、MMA、BA四元乳液共聚合成含氟聚合物乳液。对四元共聚的反应条件进行了探讨，结果表明在88℃时反应2小时为最佳反应条件。还对四元乳液共聚的乳化剂种类及用量进行了研究，结果表明在几种乳化剂搭配中，效果最好的是MS-1、SDS、FC-10所组成的复合乳化剂；乳化剂用量控制在单体总重的5％左右为佳。通过正交实验探讨了各种单体用量对乳液性能的影响，结果表明对凝胶量影响最显著的是功能性单体的用量，而含氟单体的用量对产品的吸水率和表面张力有较大影响。对乳液产品的差热示差扫描测试结果表明其玻璃化转变温度在26℃左右，这与它的最低成膜温度测试结果很接近。
第三是氟碳纳米复合环保涂料的试配。使用改性纳米TiO_2粉末作为颜料，含氟聚合物乳液作为成膜物，添加各种助剂配制涂料。确定了涂料的配方和制备工艺。涂料的性能测试结果表明氟碳纳米复合环保涂料的性能已达到国家合成树脂乳液外墙涂料的标准，而且其性能明显好于普通纯丙乳液外墙涂料。还探讨了纳米颜料用量对涂料遮盖力的影响，结果表明其用量为25％左右时涂料遮盖力最强。推导出了计算颜料CPVC的公式，并根据该公式计算出本研究中所用的纳米TiO_2颜料的CPVC为0.42。
In this paper,a kind of environmental friendly nano-composite coating which can be used for high performance exterior wall coating is studied.The paper mainly includes the contents as follows.
The first is the preparation of nanoscale pigment.Nanoscale titanium dioxide powder is prepared in terms of sol-gel process with TI(OC4H9) as raw material.The experiment results show that the productivity of nanoscale titanium dioxide is the highest when PH value of the hydrolysis system is about 2.5.TEM photoes show that the products'sizes are between 50-100nm.XRD tests indicate the crystal style of the products is rutile type.In order to apply nanoscale titanium dioxide to coating as pigment,it must be modified.The nanoscale particles are modified in terms of esterifying reaction.silane coupling agent and organic titanate coupling agent.The activation index and contact angle test results of the products prove the sequence of hydrophobic modification effect: organic titanate coupling agent modification) silane coupling agent modification esterifying reaction modification.
The second is the synthesis of emulsion containing fluorine.A kind of acrylate copolymer emulsion containing fluorine is prepared.with hexafluorobutyl mathacrylate, hexafluorobutyl acrylic acid,butyl acrylate.methyl methylacrylate as ingredients.The experiments indicate that the best coplymerization reaction conditions are 88℃ and 2 hours.Among several kinds of emulsifiers.the experiment results prove that the composite emulsifier of MS-l,SDS,FC-10 is the best and it's best amount is 5%.The orthogonality experiment results show that the amount of functional monomer has a remarkable influence on gel amount and the amount of monomer containing fluorine has deep influence on products'surface tension and water adsorption.The DSC test results indicate that emulsion products'Tg is about 26 ℃,this temperature is close to its'MFT test results.
The third is the development of environmental friendly nano-composite coating containing fluorine.The coating is developed with modified nanoscale titanium dioxide, emulsion containing fluorine and additives as materials.The
coating's formulation is determined in terms of experiments. The performance test results of the coating indicate that it's performances are up to the national standard of synthetic resin emulsion coatings for exterior wall.The coating's performances are superior to aery late emulsion coating for exterior wall.The hiding power of the coating is the best when the amount of nanoscale pigment is 25%.A formula is deduced to calculate pigment's CPVC,according to the formula,we calculate that the CPVC of nanoscale titanium dioxide powder is 0.42.
第一是纳米颜料的制备。使用溶胶一凝胶法以钛酸丁酯为原料制备了纳米TiO_2粉末。实验结果表明水解体系的PH值在2.5左右时纳米TiO_2的产率最高，透射电镜测试表明产品粒径在50～100nm之间，X衍射测试表明产品晶型为金红石型。为了使纳米TiO_2粉末达到作为涂料颜料的要求，对其进行了改性。使用三种改性方法对纳米粒子改性，改性产品的活化指数和接触角测试结果均表明亲油性改性的效果：钛酸酯偶联剂改性＞硅烷偶联剂改性＞类酯化改性。
第二是含氟聚合物乳液的合成。使用甲基丙烯酸六氟丁酯、丙烯酸六氟丁酯、MMA、BA四元乳液共聚合成含氟聚合物乳液。对四元共聚的反应条件进行了探讨，结果表明在88℃时反应2小时为最佳反应条件。还对四元乳液共聚的乳化剂种类及用量进行了研究，结果表明在几种乳化剂搭配中，效果最好的是MS-1、SDS、FC-10所组成的复合乳化剂；乳化剂用量控制在单体总重的5％左右为佳。通过正交实验探讨了各种单体用量对乳液性能的影响，结果表明对凝胶量影响最显著的是功能性单体的用量，而含氟单体的用量对产品的吸水率和表面张力有较大影响。对乳液产品的差热示差扫描测试结果表明其玻璃化转变温度在26℃左右，这与它的最低成膜温度测试结果很接近。
第三是氟碳纳米复合环保涂料的试配。使用改性纳米TiO_2粉末作为颜料，含氟聚合物乳液作为成膜物，添加各种助剂配制涂料。确定了涂料的配方和制备工艺。涂料的性能测试结果表明氟碳纳米复合环保涂料的性能已达到国家合成树脂乳液外墙涂料的标准，而且其性能明显好于普通纯丙乳液外墙涂料。还探讨了纳米颜料用量对涂料遮盖力的影响，结果表明其用量为25％左右时涂料遮盖力最强。推导出了计算颜料CPVC的公式，并根据该公式计算出本研究中所用的纳米TiO_2颜料的CPVC为0.42。
In this paper,a kind of environmental friendly nano-composite coating which can be used for high performance exterior wall coating is studied.The paper mainly includes the contents as follows.
The first is the preparation of nanoscale pigment.Nanoscale titanium dioxide powder is prepared in terms of sol-gel process with TI(OC4H9) as raw material.The experiment results show that the productivity of nanoscale titanium dioxide is the highest when PH value of the hydrolysis system is about 2.5.TEM photoes show that the products'sizes are between 50-100nm.XRD tests indicate the crystal style of the products is rutile type.In order to apply nanoscale titanium dioxide to coating as pigment,it must be modified.The nanoscale particles are modified in terms of esterifying reaction.silane coupling agent and organic titanate coupling agent.The activation index and contact angle test results of the products prove the sequence of hydrophobic modification effect: organic titanate coupling agent modification) silane coupling agent modification esterifying reaction modification.
The second is the synthesis of emulsion containing fluorine.A kind of acrylate copolymer emulsion containing fluorine is prepared.with hexafluorobutyl mathacrylate, hexafluorobutyl acrylic acid,butyl acrylate.methyl methylacrylate as ingredients.The experiments indicate that the best coplymerization reaction conditions are 88℃ and 2 hours.Among several kinds of emulsifiers.the experiment results prove that the composite emulsifier of MS-l,SDS,FC-10 is the best and it's best amount is 5%.The orthogonality experiment results show that the amount of functional monomer has a remarkable influence on gel amount and the amount of monomer containing fluorine has deep influence on products'surface tension and water adsorption.The DSC test results indicate that emulsion products'Tg is about 26 ℃,this temperature is close to its'MFT test results.
The third is the development of environmental friendly nano-composite coating containing fluorine.The coating is developed with modified nanoscale titanium dioxide, emulsion containing fluorine and additives as materials.The
coating's formulation is determined in terms of experiments. The performance test results of the coating indicate that it's performances are up to the national standard of synthetic resin emulsion coatings for exterior wall.The coating's performances are superior to aery late emulsion coating for exterior wall.The hiding power of the coating is the best when the amount of nanoscale pigment is 25%.A formula is deduced to calculate pigment's CPVC,according to the formula,we calculate that the CPVC of nanoscale titanium dioxide powder is 0.42.
引文
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[30] H Washita, M Kanba. New fluoropolymers for environmentally friendly coating. Proceeding of 17th international conference in organic coatings science and technology, 1991. 347-367
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[2] 张保利，王燕，朱柯．中国建筑涂料的发展概况及趋势．涂料工业，1998增刊：10-12
[3] 汪维．高性能外墙建筑涂料用树脂的开发．涂料工业，1998(10)：14-15
[4] 冯啸吟，冯汉保编著．涂料化学．北京：科学出版社，1997．35-41
[5] 李同信．有机氟涂料的理论分析．全面腐蚀控制，2001，13(4)：38-41
[6] 袁绍嘏，刘洪珠，张英．氟碳聚合物的高性能及应用．现代涂料与涂装，2000(4)：7—9
[7] 边蕴静．低表面能防污涂料的最新进展．化工新型材料，2000(11)：9-12
[8] 邹德荣．聚四氟乙烯防粘涂层的应用．上海涂料，2002(1)：22-24
[9] 边蕴静．氟碳树脂涂料．中国涂料，2000(6)：22—26
[10] John Schheirs. The new development of fluoropolymer coatings. Polymeric materials-encyclopedia, 1996(4): 2498-2506
[11] Akihiko Asakawa, Masao Unoki, Takao Hirono. Waterborne fluoropolymer for paint use. Journal of fluorine chemistry, 2002(104): 47-51
[12] Takashi Takayanagi, Masaaki Yamabe. Progress of fluoropolymers on coating applications development of mineral spirit soluble polymer and aqueous dispersion. Progress in organic coating,2000(40): 185-190
[13] Seiji Munekata. Fluoropolymers as coating materials. Progress in organic coatings,1988(16): 113-134
[14] G Kojima, M Yamabe. Properties and applications of fluoropolymers for coatings. Proceeding of 11th international conference in organic coatings science and technology, 1985. 120-128
[15] 徐龙贵．氟树脂研究动向．电镀与涂饰，2001，20(4)：30—34
[16] 朱东．氟涂料的现状与发展．首届氟树脂与氟涂料技术研讨会论文集．长沙，1999．3—5
[17] Moore G. waterborne crosslinkable fluorochemical coating. Surface coating internatonal, 1995(9): 377-379
[18] 程启朝，王国伟．我国氟涂料的现状与思考．现代涂料与涂装，2001(5)：22—23
[19] 刘洪珠，金宇飞．涂料用氟碳树脂乳液．第三届氟涂料发展战略及技术研讨会论文集，2002．46—48
[20] Matsumoto H. Fluorine resin coating. Kogyo Zairyo, 1989, 37(7): 55-59
[21] Stefano Turri. Chemical approaches toward the definition of new high-performance fluorocoatings. Progress in organic coatings, 1997(32): 205-213
[22] 徐祖顺．含氟聚合物乳液的研制和应用．功能高分子学报，2000，13(2)：229-233
[23] 王猛，施宪法，王静芝．水性含氟树脂涂料．有机氟工业，2002(2)：3-8
[24] 余樟清．涂料用含氟聚合物乳液的研究和应用．高分子通报，2000(6)：65-69
[25] 程时远，陈艳军，王康丽．含氟丙烯酸酯三元共聚物乳液的研究．高分子学报，2002(5)：560-565
[26] 陈沛智，陈艳军，严斌．甲基丙烯酸全氟烷基乙酯与丙烯酸酯共聚物乳液的制备．涂料工业，2002(10)：11-13
[27] 黄之祥．倡导开发环保型氟树脂涂料．涂料工业，2002(9)：34-36
[28] Yamauchi M, Hirono J. the evaluation of new fluoropolymer emulsion for exterior paint use. Surface coating international. 1996, 79(7): 312-318
[29] Ciardelli F, Aglietto M.Copolymerization of some fluoromonomers. Progress in organic coatings, 1997, 32: 43-51
[30] H Washita, M Kanba. New fluoropolymers for environmentally friendly coating. Proceeding of 17th international conference in organic coatings science and technology, 1991. 347-367
[31] Kuwamura S Hibi.Waterborne fluorinated polyolefins in coating. Surface coating intematonal. 1995(11): 525-528
[32] Brady R F Jr.Self-assembled waterborne fluoropolymer coatings for marine fouling resistance. Surface coating international, 1999(120): 582-585
[33] Robert F, Brandy Jr. properties which influence marine fouling resistance in polymers coating silicon and fluorine. Progress in organic coatings, 1999(35): 31-35
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