WO2022160853A1 - 一种紫外响应香豆素控释和自修复的防污涂料的制备方法 - Google Patents

一种紫外响应香豆素控释和自修复的防污涂料的制备方法 Download PDF

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WO2022160853A1
WO2022160853A1 PCT/CN2021/129498 CN2021129498W WO2022160853A1 WO 2022160853 A1 WO2022160853 A1 WO 2022160853A1 CN 2021129498 W CN2021129498 W CN 2021129498W WO 2022160853 A1 WO2022160853 A1 WO 2022160853A1
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coumarin
weight
self
responsive
dihydroxycoumarin
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PCT/CN2021/129498
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English (en)
French (fr)
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张庆华
佟哲名
詹晓力
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浙江大学衢州研究院
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Priority to US17/927,756 priority Critical patent/US20230212419A1/en
Publication of WO2022160853A1 publication Critical patent/WO2022160853A1/zh

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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Definitions

  • the invention relates to marine antifouling paint technology, in particular to an antifouling paint with controlled release and self-repairing of ultraviolet responsive coumarin and a preparation method thereof.
  • the means to solve the problem of marine biofouling include mechanical cleaning, underwater cleaning, and application of marine antifouling paint, among which the simplest and most effective method is to apply marine antifouling paint.
  • Low surface energy marine antifouling coatings mainly refer to organic silicon and organic fluorine antifouling coatings.
  • silicon fluorine it is difficult for marine organisms to adhere to the surface of the coating. Even if the adhesion is not firm, it is easy to fall off under the action of water flow or other external forces. , but it relies more on the external water flow to wash, and the static antifouling effect is limited, so the method of physically compounding antifouling agents in it is often used.
  • the controlled release of antifouling agents is a more difficult problem to solve.
  • due to the low modulus and low surface energy characteristics of the low surface energy antifouling coating it is difficult to repair after damage.
  • the invention aims to solve the technical problems that the release of the antifouling agent of the traditional low surface energy antifouling paint is difficult to control and difficult to repair after being damaged by the outside world. Preparation method of self-healing antifouling paint.
  • the solution of the present invention is:
  • a preparation method of an ultraviolet-responsive coumarin controlled-release and self-repairing antifouling coating comprising the following steps:
  • step (2) continue to add the dihydroxycoumarin compound of 1-20 weight part, the polyhydric alcohol or polyamine crosslinking agent of 0.1-0.2 weight part, the organic tin catalyst of 0.1-0.2 weight part, after mixing, in N 2 Atmosphere and under the same temperature condition as step (1), heat for 2h to form the polymer solution of polyurethane;
  • the weight-average molecular weight of the double-ended reactive polydimethylsiloxane is 500-5000; the double-ended group in the molecular formula refers to: hydroxypropyl, aminopropyl, and epoxy group. one or more.
  • the polyisocyanate is diisocyanate or triisocyanate, specifically: one of diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and triphenylmethane triisocyanate one or more.
  • the organic dilution solvent refers to one or more of tetrahydrofuran, xylene, N,N-dimethylformamide and butyl acetate.
  • the dihydroxycoumarin compounds refer to: 4,7-dihydroxycoumarin, 5,7-dihydroxycoumarin, 6,7-dihydroxycoumarin, 5,7-dihydroxycoumarin Dihydroxy-4-methylcoumarin, 7,8-dihydroxy-4-methylcoumarin, 7-dihydroxypropyl-4-methylcoumarin, 7-dihydroxybutyl-4- A composition of one or more of methylcoumarins.
  • the polyol or polyamine crosslinking agent refers to one or more of glycerol, butanediol, triethylamine, and hexamethylenediamine.
  • the organotin catalyst refers to one or more of dibutyltin dilaurate, dibutyltin acetoacetate, dibutyltin diacetate, and dibutyltin divalerate.
  • the simple coumarin compounds are coumarin or derivative compounds with a benzopyrone structure; specifically: coumarin, hydroxymethyl coumarin, methyl coumarin, methyl coumarin One or more of oxycoumarin, ethoxycoumarin, aminocoumarin, carboxycoumarin, and acetyl coumarin.
  • the present invention further provides a method for using the UV-responsive coumarin controlled-release and self-healing antifouling paint prepared by the aforementioned method, comprising the following steps:
  • the antifouling paint is evenly coated on the surface to be sprayed by air spraying, and the coating thickness of the wet film is 250-350 ⁇ m;
  • Coumarin and its derivatives respond to ultraviolet light, and the double bond on the pyran ring can form a butane ring under the action of 365nm ultraviolet light, so that the two coumarin monomers can form two covalent bonds through covalent bonds. And this covalent bond will be broken under the action of 254nm ultraviolet light, and form two independent coumarin monomers again, which is called photodimerization and photodepolymerization of coumarin in response to ultraviolet light.
  • the present invention utilizes the properties of photodimerization of coumarin compounds under ultraviolet irradiation of 365nm wavelength and photodepolymerization under ultraviolet light of 254nm, as shown in FIG. It is then released through photodepolymerization, and has UV-responsive coumarin controlled release properties. In addition, through the photodimerization of 365nm ultraviolet light on the coumarin compounds on the polymer chain, the coating has ultraviolet self-healing properties.
  • the antifouling coating made by the present invention has the advantages of controllable release of coumarin-based green antifouling agents in response to external ultraviolet stimuli and self-healing of the coating, overcoming the control of the release of traditional antifouling agents in the antifouling coating. Difficult and low surface energy antifouling coatings are not easy to repair after damage.
  • the present invention can meet the anti-fouling application requirements of light-transmitting parts in shallow seas of various ships, marine engineering equipment and structural facilities, marine pasture breeding nets, and the like.
  • the antifouling coating prepared by the invention has the properties of UV-responsive coumarin controlled release and self-repair, can prolong the service life and enhance the application performance in the complex real sea environment.
  • Fig. 1 Mechanism of UV-responsive coumarin controlled release and self-healing antifouling coating with low surface energy
  • the test method is carried out with reference to the national standard GB/T 5370-2007 "Anti-fouling paint sample test method for shallow sea immersion".
  • the base material used is a low-carbon steel plate with a thickness of 3 mm and a size of 350 mm ⁇ 250 mm.
  • the immersion period in the shallow sea is 3 months (August-November), and the immersion depth is 0.5 m.
  • Class I Very thin mucus is confirmed to adhere, but no animal species adherence is confirmed
  • Level V The entire coating film confirms the adhesion of the animal species.
  • the distance between the ultraviolet lamp (Hubang Electronic Technology Co., Ltd. HB-UVC-250W) and the coating is 1m, and the immersion depth is 1m.
  • the coumarin concentration was measured by UV spectrophotometer.
  • the coumarin release rate of the coatings in water was tested under sunlight, the immersion depth was 1m, and the released coumarin concentration was detected by an ultraviolet spectrophotometer.
  • the prepared coated strips (3 ⁇ 3 ⁇ 0.1 cm) were completely cut off and then connected, respectively irradiated with 365 nm ultraviolet light in water for 4 h, and the cut marks were observed with an optical microscope.
  • Class I The splines are connected, and the incision is difficult to observe with the naked eye and difficult to observe through a microscope
  • Class II The splines are connected, and the incision is difficult to observe with the naked eye, but can be observed through a microscope
  • Grade III The splines are connected, and the incision can be observed with the naked eye
  • the UV-responsive coumarin controlled-release and self-healing antifouling coatings prepared in the various embodiments of the present invention have a coumarin release rate under UV light (254 nm) irradiation.
  • the release rate was significantly higher than that under dark conditions, proving its controlled release performance in response to UV light.
  • the coumarin release performance of the coating under sunlight is also significantly better than that under the dark conditions, which further proves that the coating can be used in ultraviolet and sunlight. Controlled release of coumarins.
  • the results of the real sea immersion antifouling experiment show that the antifouling coating has a good antifouling effect in the real sea.
  • UV self-healing experiments show that the coating has better self-healing properties under UV light (365 nm).
  • the above experimental results prove that the antifouling coating prepared by the present invention can meet the antifouling application requirements of light-transmitting parts in shallow seas of various ships, marine engineering equipment and structural facilities, marine pasture breeding nets and the like.

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Abstract

紫外响应香豆素控释和自修复的防污涂料的制备方法，包括：将双端基反应性聚二甲基硅氧烷、多异氰酸酯和有机稀释溶剂，反应得到异氰酸酯基封端的预聚物；继续加入二羟基香豆素类化合物、多元醇或多元胺交联剂、有机锡催化剂，反应形成聚氨酯的聚合物溶液；继续加入简单香豆素类化合物，混匀后以365nm紫外光照射，得到防污涂料。

Description

一种紫外响应香豆素控释和自修复的防污涂料的制备方法 技术领域
本发明涉及海洋防污涂料技术，特别涉及一种紫外响应香豆素控释和自修复的防污涂料及制备方法。
背景技术
我国陆地海岸线长达1.8万多公里，从北到南海洋环境复杂多变。船舶在海洋环境中航行时，由于长期浸泡在海水中，船体部分容易受到海洋生物的污损。据统计，全世界已发现的海洋污损生物有4000～5000种，而中国沿岸已记录的就有650种之多。海洋污损生物种类之多，分布范围之广，使得浸入海水中的轮船、海上钻井、勘探设备、码头、水产养殖笼等人工设施表面更容易发生海洋生物污损，给人类的生产和生活带来了很大影响，造成巨大经济损失。
解决海洋生物污损问题的手段有机械清理，水下清理，涂覆海洋防污涂料等，其中最简单也是最有效的方法就是涂覆海洋防污涂料。
从海洋防污涂料的发展历史来看，原先采用的多为通过释放杀菌剂对海洋生物进行毒杀，其中以三丁基锡自抛光涂料效果最好。然而由于有机锡防污剂能在水中稳定积累，海洋生物体摄入会引发畸形，并可能进入食物链，因此国际海事组织已于2008年1月起禁止全球范围内使用有机锡防污涂料。随着人们对海洋环境的日益重视，作为有机锡替代品的低毒性亚铜防污涂料因对海洋环境有危害而被部分禁止使用。目前市场需要无毒、环保的新型海洋防污涂料，低表面能防污涂料就是其中重要的一类。
低表面能海洋防污涂料主要指有机硅和有机氟防污涂料，利用硅氟的低表面能，海洋生物难以在涂层表面附着，即使附着也不牢固，在水流或其他外力作用下容易脱落，但其较依赖外界水流冲刷，静态防污效果有限，因此常采用在其内部物理复合防污剂的方法。但防污剂的可控释放是比较难以解决的问题。同时由于低表面能防污涂层的低模量和低表面能特性，损坏后难以修复。
发明内容
本发明要解决的是传统低表面能防污涂料的防污剂释放难以控制，受到外界损害后难以修复的技术问题，为克服现有技术的不足，提供一种紫外响应香豆素控释和自修复防污涂料制备方法。
为解决技术问题，本发明的解决方案是：
一种紫外响应香豆素控释和自修复的防污涂料的制备方法，包括以下步骤：
(1)取10-50重量份的双端基反应性聚二甲基硅氧烷、1-10重量份的多异氰酸酯和10-100份的有机稀释溶剂，混匀后在N 2氛围和60-80℃条件下加热4h，得到异氰酸酯基封端的预聚物；
(2)继续加入1-20重量份的二羟基香豆素类化合物、0.1-0.2重量份的多元醇或多元胺交联剂、0.1-0.2重量份的有机锡催化剂，混匀后在N 2氛围和与步骤(1)相同的温度条件下加热2h，形成聚氨酯的聚合物溶液；
(3)继续加入1-20重量份的简单香豆素类化合物，混匀后以365nm紫外光照射4h，得到防污涂料。
本发明中，所述双端基反应性聚二甲基硅氧烷的重均分子量为500-5000；其分子式中的双端基是指：羟丙基、氨丙基、环氧基中的一种或多种。
本发明中，所述多异氰酸酯是二异氰酸酯或、三异氰酸酯，具体是指：二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、三苯基甲烷三异氰酸酯中的一种或多种。
本发明中，所述有机稀释溶剂是指：四氢呋喃、二甲苯、N,N-二甲基甲酰胺、乙酸丁酯中的一种或多种。
本发明中，所述二羟基香豆素类化合物是指：4,7-二羟基香豆素、5,7-二羟基香豆素、6,7-二羟基香豆素、5,7-二羟基-4-甲基香豆素、7,8-二羟基-4-甲基香豆素、7-二羟基丙基-4-甲基香豆素、7-二羟基丁基-4-甲基香豆素中的一种或多种的组合物。
本发明中，所述多元醇或多元胺交联剂是指：丙三醇、丁二醇、三乙胺、己二胺中的一种或多种。
本发明中，所述有机锡催化剂是指：二月桂酸二丁基锡、乙酰乙酸二丁基锡、二乙酸二丁基锡、二戊酸二丁基锡中的一种或多种。
本发明中，所述简单香豆素类化合物是具有苯并吡喃酮结构的香豆素或衍生化合物；具体是指：香豆素、羟甲基香豆素、甲基香豆素、甲氧基香豆素、乙氧基香豆素、氨基香豆素、羧基香豆素、乙酰基香豆素中的一种或多种。
本发明进一步提供了前述方法制备获得的紫外响应香豆素控释和自修复的防污涂料的使用方法，包括以下步骤：
(1)清理干净待喷涂表面；
(2)将所述防污涂料以空气喷涂的方式均匀涂覆在待喷涂表面，湿膜的涂覆厚度为250-350μm；
(3)在通风干燥的室温条件下干燥48小时，得到干燥涂膜。
发明原理描述：
香豆素及其衍生物对紫外光具有响应作用，其吡喃环上的双键能够在365nm紫外线的作用下形成丁烷环，从而将2个香豆素单体通过共价键作用形成二聚化合物；而这种共价键又会在254nm紫外线的作用下断裂，重新形成2个独立的香豆素单体，称为香豆素对紫外响应的光二聚和光解聚作用。
基于在不同紫外线下香豆素的光二聚和光解聚作用，制备了具有紫外线响应的可控香豆素释放性能的智能海洋防污涂料。游离香豆素在365nm紫外线下通过光二聚作用以可逆共价键的形式结合在涂层中，并通过254nm UV作用破坏前述的可逆共价键，香豆素自涂层释放，以防御海洋污损生物在表面附着生长。
本发明利用香豆素类化合物在365nm波长的紫外线照射下光二聚，254nm紫外线下光解聚的性质，如图1所示，将游离香豆素类化合物通过光二聚化学负载至聚合物链，再通过光解聚释放，具有紫外响应香豆素控释性能。另外，通过365nm紫外光对聚合物链上香豆素类化合物之间的光二聚作用，使该涂层具有紫外自修复性能。
与现有技术相比，本发明的有益效果是：
1、本发明制成的防污涂层，具有香豆素类绿色防污剂对外界紫外刺激响应可控释放和涂层自修复的优点，克服传统防污剂在防污涂层内释放控制难、低表面能防污涂层破坏后不易修复的问题。
2、本发明可以满足各类舰船、海洋工程装备与结构设施、海洋牧场养殖网具等的浅海透光部位的防污应用需求。本发明制成的防污涂层具有紫外响应香豆素控释和自修复性能，能够延长使用寿命，增强在复杂实海环境的应用性能。
附图说明
图1紫外响应香豆素控释和自修复的低表面能防污涂层的机理；
具体实施方式
以下结合具体实施例和比较例对发明作进一步详细说明。实施例可以使本专业的专业技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
本实施例涉及的紫外响应香豆素控释和自修复的防污涂料的制备和使用方法如下：
(1)取10g的双羟丙基封端聚二甲基硅氧烷(分子量500)、1g的六亚甲基二异氰酸酯(HDI)、10g四氢呋喃，混匀后在N 2氛围下60℃加热4h形成异氰酸酯基封端的预聚物；
(2)加入1g的4,7-二羟基香豆素、0.1g的三乙胺、0.1g的二乙酸二丁基锡，混匀后在N 2氛围下60℃加热2h形成聚氨酯聚合物溶液；
(3)加入1g香豆素搅拌均匀，365nm紫外光照射4h，得到防污涂料。
(4)将防污涂料以空气喷涂的方式均匀涂覆在试样的待喷涂表面，涂覆厚度为250μm左右(湿膜)；在通风干燥的室温环境下干燥48小时，形成干燥涂膜。
实施例2
本实施例涉及的紫外响应香豆素控释和自修复的防污涂料的制备和使用方法如下：
(1)取20g的双环氧基封端聚二甲基硅氧烷(分子量1000)、3g的异佛尔酮二异氰酸酯(IPDI)、60g二甲苯，混匀后在N 2氛围下75℃加热4h形成异氰酸酯基封端的预聚物；
(2)加入10g的5,7-二羟基-4-甲基香豆素、0.15g的丁二醇、0.15g的二月桂酸二丁基锡，混匀后在N 2氛围下75℃加热2h形成聚氨酯聚合物溶液；
(3)加入10g羟甲基香豆素搅拌均匀，365nm紫外光照射4h，得到防污涂料。
(4)将防污涂料以空气喷涂的方式均匀涂覆在试样的待喷涂表面，涂覆厚度为300μm左右(湿膜)；在通风干燥的室温环境下干燥48小时，形成干燥涂膜。
实施例3
本实施例涉及的紫外响应香豆素控释和自修复的防污涂料的制备和使用方法如下：
(1)取30g的双羟丙基封端聚二甲基硅氧烷(分子量3000)、5g的二苯基甲烷二异氰酸酯(MDI)、100g乙酸丁酯，混匀后在N 2氛围下80℃加热4h形成异氰酸酯基封端的预聚物；
(2)加入15g的7-二羟基丙基-4-甲基香豆素、0.18g的丙三醇、0.18g的乙酰乙酸二丁基锡，混匀后在N 2氛围下80℃加热2h形成聚氨酯聚合物溶液；
(3)加入15g甲基香豆素搅拌均匀，365nm紫外光照射4h，得到防污涂料。
(4)将防污涂料以空气喷涂的方式均匀涂覆在试样的待喷涂表面，涂覆厚度为350μm左右(湿膜)；在通风干燥的室温环境下干燥48小时，形成干燥涂膜。
实施例4
本实施例涉及的紫外响应香豆素控释和自修复的防污涂料的制备和使用方法如下：
(1)取50g的双氨丙基封端聚二甲基硅氧烷(分子量5000)、10g的三苯基甲烷三异氰酸酯、100gN,N-二甲基甲酰胺，混匀后在N 2氛围下60℃加热4h形成异氰酸酯基封端的预聚物；
(2)加入20g的7-二羟基丁基-4-甲基香豆素、0.2g的己二胺、0.2g的二戊酸二丁基锡，混匀后在N 2氛围下60℃加热2h形成聚氨酯聚合物溶液；
(3)加入20g甲氧基香豆素搅拌均匀，365nm紫外光照射4h，得到防污涂料。
(4)将防污涂料以空气喷涂的方式均匀涂覆在试样的待喷涂表面，涂覆厚度为350μm左右(湿膜)；在通风干燥的室温环境下干燥48小时，形成干燥涂膜。
性能评价结果：
(1)实海防污性能
测试方法参照国标GB/T 5370-2007《防污漆样板浅海浸泡试验方法》进行。所用基材为3mm厚、尺寸为350mm×250mm的低碳钢板，浅海浸泡周期为3个月(8月-11月)，浸泡深度为0.5m。
Ⅰ级：确认附着极薄的粘液，但未确认动物种的附着
Ⅱ级：确认附着粘液，但未确认动物种的附着
Ⅲ级：确认附着厚的粘液，但未确认动物种的附着
Ⅳ级：确认动物种的污损
Ⅴ级：涂膜整体确认动物种的附着。
实海防污性能测试结果见表1。
(2)香豆素释放性能
通过测试水中涂层分别在254nm紫外光和黑暗环境下的香豆素释放速率，紫外灯(沪帮电子科技有限公司HB-UVC-250W)与涂层距离为1m，浸泡深度1m，释放出的香豆素浓度以紫外分光光度计检测。
测试水中涂层分别在太阳光环境下的香豆素释放速率，浸泡深度1m，释放出的香豆素浓度以紫外分光光度计检测。
香豆素释放性能测试结果见表1。
(3)紫外自修复性能表征
将制备的涂层样条(3×3×0.1cm)完全切断后连接，分别在水中使用365nm紫外光照射4h，使用光学显微镜观察切断的痕迹。
Ⅰ级：样条有连接，切痕难以用肉眼观察，通过显微镜难以观察
Ⅱ级：样条有连接，切痕难以用肉眼观察，通过显微镜可观察
Ⅲ级：样条有连接，切痕可用肉眼观察
Ⅳ级：样条无连接
紫外自修复性能表征测试结果见表1。
表1紫外响应香豆素控释和自修复的防污涂层试验结果
Figure PCTCN2021129498-appb-000001
验证试验总结：
从表1的试验结果中可以看出，本发明各实施例中所制备的紫外响应香豆素控释和自修复的防污涂层，在紫外光(254nm)照射下的香豆素释放速率明显高于黑暗条件下的释放速率，证明其具有对紫外线响应的可控释放性能。在实海的太阳光条件下，由于太阳光光谱中亦包括254nm紫外线部分，涂层在太阳光下的香豆素释放性能亦明显优于黑暗条件，进一步证明了该涂层在紫外、太阳光下的香豆素的可控释放。实海浸泡防污实验结果显示该防污涂层具有较好的实海防污效果。紫外自修复实验显示该涂层在紫外光(365nm)下具有较好的自修复性能。上述实验结果证明本发明制备的防污涂层可以满足各类舰船、海洋工程装备与结构设施、海洋牧场养殖网具等的浅海透光部位的防污应用需求。
本发明已详细描述并在实施例部分以举例方式说明了本发明的具体实施方案，但本发明还可作出各种修改方案和替代形式。应当理解，本发明并不局限于所公开的具体形式。本发明涵盖落入由所附权利要求限定的本发明的实质和范围内的所有修改方案、等同方案和替代方案。

Claims (9)

  1. 一种紫外响应香豆素控释和自修复的防污涂料的制备方法，其特征在于，包括以下步骤：
    (1)取10-50重量份的双端基反应性聚二甲基硅氧烷、1-10重量份的多异氰酸酯和10-100份的有机稀释溶剂，混匀后在N2氛围和60-80℃条件下加热4h，得到异氰酸酯基封端的预聚物；
    (2)继续加入1-20重量份的二羟基香豆素类化合物、0.1-0.2重量份的多元醇或多元胺交联剂、0.1-0.2重量份的有机锡催化剂，混匀后在N2氛围和与步骤(1)相同的温度条件下加热2h，形成聚氨酯的聚合物溶液；
    (3)继续加入1-20重量份的简单香豆素类化合物，混匀后以365nm紫外光照射4h，得到防污涂料。
  2. 根据权利要求1所述的方法，其特征在于，所述双端基反应性聚二甲基硅氧烷的重均分子量为500-5000；其分子式中的双端基是指：羟丙基、氨丙基、环氧基中的一种或多种。
  3. 根据权利要求1所述的方法，其特征在于，所述多异氰酸酯是二异氰酸酯或、三异氰酸酯，具体是指：二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、三苯基甲烷三异氰酸酯中的一种或多种。
  4. 根据权利要求1所述的方法，其特征在于，所述有机稀释溶剂是指：四氢呋喃、二甲苯、N,N-二甲基甲酰胺、乙酸丁酯中的一种或多种。
  5. 根据权利要求1所述的方法，其特征在于，所述二羟基香豆素类化合物是指：4,7-二羟基香豆素、5,7-二羟基香豆素、6,7-二羟基香豆素、5,7-二羟基-4-甲基香豆素、7,8-二羟基-4-甲基香豆素、7-二羟基丙基-4-甲基香豆素、7-二羟基丁基-4-甲基香豆素中的一种或多种的组合物。
  6. 根据权利要求1所述的方法，其特征在于，所述多元醇或多元胺交联剂是指：丙三醇、丁二醇、三乙胺、己二胺中的一种或多种。
  7. 根据权利要求1所述的方法，其特征在于，所述有机锡催化剂是指：二月桂酸二丁基锡、乙酰乙酸二丁基锡、二乙酸二丁基锡、二戊酸二丁基锡中的一种或多种。
  8. 根据权利要求1所述的方法，其特征在于，所述简单香豆素类化合物是具有苯并吡喃酮结构的香豆素或衍生化合物；具体是指：香豆素、羟甲基香豆素、甲基香豆素、甲氧基香豆素、乙氧基香豆素、氨基香豆素、羧基香豆素、乙酰基香豆素中的一种或多种。
  9. 权利要求1所述方法制备获得的紫外响应香豆素控释和自修复的防污涂料的使用方法，其特征在于，包括以下步骤：
    (1)清理干净待喷涂表面；
    (2)将所述防污涂料以空气喷涂的方式均匀涂覆在待喷涂表面，湿膜的涂覆厚度为250-350μm；
    (3)在通风干燥的室温条件下干燥48小时，得到干燥涂膜。
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