低表面能及改性丙烯酸系列无毒防污涂料制备与应用研究
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摘要
在海洋中航行的船只受到海水侵蚀后会附着种类繁多的生物,并使船体表面的摩擦力明显增加,进而导致舰船航速降低,燃料消耗增大,进坞维修次数增多。为防止海洋生物附着,最有效的措施是在船壳表面涂覆有毒的防污涂料。但有毒防污涂料的使用破坏了海洋的生态环境,严重威胁着人类的健康。国际海事组织已明令禁止在2008年1月1日后使用含有机锡毒物的防污涂料,随着这一禁令的实施,环境友好无毒船舶防污涂料的开发研制已经在全球范围内展开,其中无毒低表面能脱污型(fouling release)防污涂料的研究尤为引人注目。
本研究以耐候性和耐油性优异、且价格低廉的丙烯酸树脂为基础,针对海洋污损生物的附着机制,设计合成了具有低表面能等不同特性的系列改性丙烯酸树脂,并用红外光谱和凝胶色谱对合成树脂的结构及分子量进行了检测。结果表明,采用自由基溶液共聚法,可以将各种丙烯酸单体与氢氧化锌及聚硅氧烷聚合,合成出具有水解特性的丙烯酸锌树脂和聚硅氧烷改性丙烯酸树脂;也可以将有机硅单体与丙烯酸单体共聚,合成出具有低表面能特性的有机硅改性丙烯酸树脂。采用化学滴定法检测了改性丙烯酸树脂的酸值,用JY-82型接触角检测仪检测了树脂与水滴的接触角和涂膜的表面能。结果表明,合成的丙烯酸锌树脂和聚硅氧烷改性丙烯酸树脂的酸值、水解率和储存稳定性良好,具有自抛光特性;合成的有机硅改性丙烯酸树脂涂膜均匀饱满,与水的接触角可达83°,具有低表面能特性。系列改性丙烯酸树脂的合成工艺方法简便,原料来源广泛,在替代含毒防污涂料方面具有广阔的应用前景。
同时,本研究以上述系列改性丙烯酸树脂为成膜物,通过添加各种防污剂、防污助剂、颜填料、以及各类溶剂和助剂,制备了丙烯酸锌自抛光型、自抛/低表面能双重作用型和仿生无毒低表面能脱污型等三种防污涂料。依据国标GB6824-86,检测了自抛光防污涂料的铜离子渗出率,用GS-X150表面张力测定仪检测了低表面能防污涂膜的表面能,用SEM和GE5数码显微镜观察了低表面能无毒防污涂料的表面结构、涂膜形貌及其与液体接触的界面状态,并对防污涂料进行了实海试验。结果表明,本研究使用的三种防污助剂(TCPM、百菌清和敌草隆)均可减缓涂料中铜离子的渗出率,因而明显增加了涂料的防污期效与防污性能,其中TCPM的防污效果最好;微米级颜填料和纳米级SiO2粒子的加入,不仅有效地改善了涂料涂膜的强度,更主要的是通过仿照荷叶表面微观结构特征,在涂膜表面构筑出了一种微米-纳米阶层结构。这种结构,导致涂膜与液滴界面间产生了一种显微“气垫”形态,进而导致涂膜与液滴间的接触角高达150°、表面能降至6mJ/m2、且附着力达1级,为在完全环保无毒的条件下仅以仿生涂膜的物理特性防止海洋生物污损方面提供了坚实的理论与应用基础。接触角可达150°的仿生无毒海洋防污涂料,在国内外同类研究与应用方面迄今还未见报导。
最后,本研究针对海洋污损生物的附着机理、低表面能涂膜表面微米-纳米结构及其上形成“气垫”后表面润湿性及接触角的变化,提出了首先增加固体表面的粗糙度γ,使其更容易稳定地实现表面的超疏水性能,其次降低固液接触界面分数f s,以进一步提高涂膜表面的疏水性能的低表面能涂料的设计思路。实海试验的结果表明,具有微米-纳米阶层结构的涂膜具有良好的防污效果。
The ships navigating in the sea would be fouled by many types of marine life, which causes the friction force of hull surface to be increased obviously, the ships speed to be reduced and the fuel consumption and the maintenance cost of ship to be increased. In order to prevent the marine life attaching, it is the most effective that the surface of hull is coated by virulent antifouling coatings. Traditionally, fouling has been controlled by antifouling paint with tributyltin. They can accumulate in marine life and be difficult to degrade, which not only causes adverse effects in the environment, but also threatens the health of humans. The International Maritime Organization has issued ban to prohibit using antifouling coating included tributyltin after January 1, 2008. Consequently, research and development of environment benign antifouling coatings have already launched over the world.
In this paper, series modified acrylic resin with different characteristics were synthesized referring to the adhesion mechanism of marine lives. Because of superior quality and lower cost, the acrylic resin was taken as foundation material. The infrared spectroscopy and the gelatin chromatograph have been used to detect the synthetic resin structures and the molecular weight. The results indicated that various kinds of acrylic monomer can be co-polymerized with zinc hydroxide and the polysiloxane compound through controlling the craft parameters and based on the free radical solution copolymerization principle, and then the copolymer can be obtained with a compatible hydrolysis characteristic. On the other hand, the acrylic resin modified with the organosilicon and possessed low surface energy can also be synthesized with acrylic monomer and organosilicon monomer. The advantages of the synthesis process are simple and safe, widespread raw material and a broad application prospect.
The acid values of the modified acrylic resin were detected with the chemistry titrimetric method, and the contact angle between films and liquid and the surface energy of the films are examined with the JY-82 contact angle analyzer. The results showed that the performances including acid value, hydroxide value, hydrolisis rate and the storage stability are excellent, and both the zinc acrylate resin and the polysiloxane modified acrylic resin possess self-polishing characteristic. The contact angle between the film of the modified acrylic resin and water can reach to as high as 83°.
Three types of antifouling coatings have been prepared by taking the series of modified acrylic resin mentioned above as the matrix material and mixing them with the different kind of antifouling boosters, aid agents, pigments and solvents. The coatings include‘self-polishing zinc acrylate coating’,‘self-polishing/lower-surface energy coating’and‘bionic and non-toxic coating’. Based on the Chinese National Standard of GB6824-86, the Cu-ion release rates, the surface energies, the interaction between the water and the surface structures of the films have been examined with the GS-X150 surface tension analyzer, SEM and the GE5 digital microscope respectively, while the sea exposure test has also been carried out. The result showed that, all the three kinds of antifouling boosters (TCPM, Chlorothalonil and Diuron) can decrease the rates of Cu-ion release and thus increase the antifouling life and property of the coatings obviously. Besides improving the strength, additions of the micro scale pigments and the nano-scale SiO2 particles can also build up micro-nano mixed structures on the film surfaces as happened on the surface of the lotus leaf, and then a“air pad”could be found on the film surface. By existing of the air pad, the contact angles of the films can be significantly increased to as high as 150°, while the surface energies can be decreased to as low as 6mJ/m2, and the adhesion strength of the film on the matrix substances can reach to Grade I. in this case, the sea fouling lives can be retarded totally and solely by the physical mechanism. The sea exposure test confirmed that the antifouling property of the coatings has been increased considerably.
Based on the adhesion mechanism of the sea life, the micro-nano structure of the low surface energy film and the‘air pad’phenomena, as well as the physical-chemical interaction between the wettability of the surface and the contact angle, and detailed discussions on the antifouling mechanism of the low surface energy coatings have been reviewed systematically. Firstly, to increase the roughness of the solid surface can be helpful to result a super hydrophobic surface stably; secondly, to decrease the ratio of the interface between the solid and liquid can further increase the hydrophobic of the films of the low surface coatings. The results and discussions mentioned above have not been reported so far, and will be helpful to the research and application of the low surface energy and foul release coatings.
本研究以耐候性和耐油性优异、且价格低廉的丙烯酸树脂为基础,针对海洋污损生物的附着机制,设计合成了具有低表面能等不同特性的系列改性丙烯酸树脂,并用红外光谱和凝胶色谱对合成树脂的结构及分子量进行了检测。结果表明,采用自由基溶液共聚法,可以将各种丙烯酸单体与氢氧化锌及聚硅氧烷聚合,合成出具有水解特性的丙烯酸锌树脂和聚硅氧烷改性丙烯酸树脂;也可以将有机硅单体与丙烯酸单体共聚,合成出具有低表面能特性的有机硅改性丙烯酸树脂。采用化学滴定法检测了改性丙烯酸树脂的酸值,用JY-82型接触角检测仪检测了树脂与水滴的接触角和涂膜的表面能。结果表明,合成的丙烯酸锌树脂和聚硅氧烷改性丙烯酸树脂的酸值、水解率和储存稳定性良好,具有自抛光特性;合成的有机硅改性丙烯酸树脂涂膜均匀饱满,与水的接触角可达83°,具有低表面能特性。系列改性丙烯酸树脂的合成工艺方法简便,原料来源广泛,在替代含毒防污涂料方面具有广阔的应用前景。
同时,本研究以上述系列改性丙烯酸树脂为成膜物,通过添加各种防污剂、防污助剂、颜填料、以及各类溶剂和助剂,制备了丙烯酸锌自抛光型、自抛/低表面能双重作用型和仿生无毒低表面能脱污型等三种防污涂料。依据国标GB6824-86,检测了自抛光防污涂料的铜离子渗出率,用GS-X150表面张力测定仪检测了低表面能防污涂膜的表面能,用SEM和GE5数码显微镜观察了低表面能无毒防污涂料的表面结构、涂膜形貌及其与液体接触的界面状态,并对防污涂料进行了实海试验。结果表明,本研究使用的三种防污助剂(TCPM、百菌清和敌草隆)均可减缓涂料中铜离子的渗出率,因而明显增加了涂料的防污期效与防污性能,其中TCPM的防污效果最好;微米级颜填料和纳米级SiO2粒子的加入,不仅有效地改善了涂料涂膜的强度,更主要的是通过仿照荷叶表面微观结构特征,在涂膜表面构筑出了一种微米-纳米阶层结构。这种结构,导致涂膜与液滴界面间产生了一种显微“气垫”形态,进而导致涂膜与液滴间的接触角高达150°、表面能降至6mJ/m2、且附着力达1级,为在完全环保无毒的条件下仅以仿生涂膜的物理特性防止海洋生物污损方面提供了坚实的理论与应用基础。接触角可达150°的仿生无毒海洋防污涂料,在国内外同类研究与应用方面迄今还未见报导。
最后,本研究针对海洋污损生物的附着机理、低表面能涂膜表面微米-纳米结构及其上形成“气垫”后表面润湿性及接触角的变化,提出了首先增加固体表面的粗糙度γ,使其更容易稳定地实现表面的超疏水性能,其次降低固液接触界面分数f s,以进一步提高涂膜表面的疏水性能的低表面能涂料的设计思路。实海试验的结果表明,具有微米-纳米阶层结构的涂膜具有良好的防污效果。
The ships navigating in the sea would be fouled by many types of marine life, which causes the friction force of hull surface to be increased obviously, the ships speed to be reduced and the fuel consumption and the maintenance cost of ship to be increased. In order to prevent the marine life attaching, it is the most effective that the surface of hull is coated by virulent antifouling coatings. Traditionally, fouling has been controlled by antifouling paint with tributyltin. They can accumulate in marine life and be difficult to degrade, which not only causes adverse effects in the environment, but also threatens the health of humans. The International Maritime Organization has issued ban to prohibit using antifouling coating included tributyltin after January 1, 2008. Consequently, research and development of environment benign antifouling coatings have already launched over the world.
In this paper, series modified acrylic resin with different characteristics were synthesized referring to the adhesion mechanism of marine lives. Because of superior quality and lower cost, the acrylic resin was taken as foundation material. The infrared spectroscopy and the gelatin chromatograph have been used to detect the synthetic resin structures and the molecular weight. The results indicated that various kinds of acrylic monomer can be co-polymerized with zinc hydroxide and the polysiloxane compound through controlling the craft parameters and based on the free radical solution copolymerization principle, and then the copolymer can be obtained with a compatible hydrolysis characteristic. On the other hand, the acrylic resin modified with the organosilicon and possessed low surface energy can also be synthesized with acrylic monomer and organosilicon monomer. The advantages of the synthesis process are simple and safe, widespread raw material and a broad application prospect.
The acid values of the modified acrylic resin were detected with the chemistry titrimetric method, and the contact angle between films and liquid and the surface energy of the films are examined with the JY-82 contact angle analyzer. The results showed that the performances including acid value, hydroxide value, hydrolisis rate and the storage stability are excellent, and both the zinc acrylate resin and the polysiloxane modified acrylic resin possess self-polishing characteristic. The contact angle between the film of the modified acrylic resin and water can reach to as high as 83°.
Three types of antifouling coatings have been prepared by taking the series of modified acrylic resin mentioned above as the matrix material and mixing them with the different kind of antifouling boosters, aid agents, pigments and solvents. The coatings include‘self-polishing zinc acrylate coating’,‘self-polishing/lower-surface energy coating’and‘bionic and non-toxic coating’. Based on the Chinese National Standard of GB6824-86, the Cu-ion release rates, the surface energies, the interaction between the water and the surface structures of the films have been examined with the GS-X150 surface tension analyzer, SEM and the GE5 digital microscope respectively, while the sea exposure test has also been carried out. The result showed that, all the three kinds of antifouling boosters (TCPM, Chlorothalonil and Diuron) can decrease the rates of Cu-ion release and thus increase the antifouling life and property of the coatings obviously. Besides improving the strength, additions of the micro scale pigments and the nano-scale SiO2 particles can also build up micro-nano mixed structures on the film surfaces as happened on the surface of the lotus leaf, and then a“air pad”could be found on the film surface. By existing of the air pad, the contact angles of the films can be significantly increased to as high as 150°, while the surface energies can be decreased to as low as 6mJ/m2, and the adhesion strength of the film on the matrix substances can reach to Grade I. in this case, the sea fouling lives can be retarded totally and solely by the physical mechanism. The sea exposure test confirmed that the antifouling property of the coatings has been increased considerably.
Based on the adhesion mechanism of the sea life, the micro-nano structure of the low surface energy film and the‘air pad’phenomena, as well as the physical-chemical interaction between the wettability of the surface and the contact angle, and detailed discussions on the antifouling mechanism of the low surface energy coatings have been reviewed systematically. Firstly, to increase the roughness of the solid surface can be helpful to result a super hydrophobic surface stably; secondly, to decrease the ratio of the interface between the solid and liquid can further increase the hydrophobic of the films of the low surface coatings. The results and discussions mentioned above have not been reported so far, and will be helpful to the research and application of the low surface energy and foul release coatings.
引文
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