CN113150594B - 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

Info

Publication number
CN113150594B
CN113150594B CN202110123001.5A CN202110123001A CN113150594B CN 113150594 B CN113150594 B CN 113150594B CN 202110123001 A CN202110123001 A CN 202110123001A CN 113150594 B CN113150594 B CN 113150594B
Authority
CN
China
Prior art keywords
coumarin
antifouling
ultraviolet
antifouling paint
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110123001.5A
Other languages
English (en)
Other versions
CN113150594A (zh
Inventor
张庆华
佟哲名
詹晓力
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quzhou Research Institute of Zhejiang University
Original Assignee
Quzhou Research Institute of Zhejiang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quzhou Research Institute of Zhejiang University filed Critical Quzhou Research Institute of Zhejiang University
Priority to CN202110123001.5A priority Critical patent/CN113150594B/zh
Publication of CN113150594A publication Critical patent/CN113150594A/zh
Priority to PCT/CN2021/129498 priority patent/WO2022160853A1/zh
Priority to US17/927,756 priority patent/US20230212419A1/en
Application granted granted Critical
Publication of CN113150594B publication Critical patent/CN113150594B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/6765—Low-molecular-weight compounds containing the unsaturation at least partially in a cyclic ring having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—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
    • C08G18/753—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Abstract

本发明涉及海洋防污涂料技术，旨在提供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：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。本发明涂料形成的防污涂层，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。可以满足各类浅海透光构建的防污应用需求，延长使用寿命，增强在复杂实海环境的应用性能。

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
本发明要解决的技术问题是，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的防污涂料的制备方法。
为解决技术问题，本发明的解决方案是：
提供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。
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料，其使用后形成的涂膜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。本发明的涂料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N2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N2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N2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N2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N2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N2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、100g N,N-二甲基甲酰胺，混匀后在N2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N2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。
评级判断依据：
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
将带涂层的样条(3×3×0.1cm)完全切断后再沿切口重新对接，然后分别在水中使用365nm紫外光照射4h，使用光学显微镜观察切断的痕迹。
评级判断依据：
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 BDA0002922717260000061
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。
CN202110123001.5A 2021-01-29 2021-01-29 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 Active CN113150594B (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202110123001.5A CN113150594B (zh) 2021-01-29 2021-01-29 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
PCT/CN2021/129498 WO2022160853A1 (zh) 2021-01-29 2021-11-09 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
US17/927,756 US20230212419A1 (en) 2021-01-29 2021-11-09 Preparation method for ultraviolet-responsive coumarin controlled-release and self-repairing anti-fouling paint

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110123001.5A CN113150594B (zh) 2021-01-29 2021-01-29 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

Publications (2)

Publication Number Publication Date
CN113150594A CN113150594A (zh) 2021-07-23
CN113150594B true CN113150594B (zh) 2022-06-21

Family

ID=76879021

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110123001.5A Active CN113150594B (zh) 2021-01-29 2021-01-29 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

Country Status (3)

Country Link
US (1) US20230212419A1 (zh)
CN (1) CN113150594B (zh)
WO (1) WO2022160853A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113150594B (zh) * 2021-01-29 2022-06-21 浙江大学衢州研究院 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
CN114574047A (zh) * 2022-03-10 2022-06-03 合肥洲创机械制造有限公司 一种机械设备加工件表面防锈涂料的制备方法
CN115851097B (zh) * 2022-12-21 2023-08-15 浙江大学 一种多孔液体注入的光响应超润滑防污涂料的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153856A (zh) * 2011-02-24 2011-08-17 中山大学 一种光致可逆自修复聚氨酯薄膜及其制备和修复方法
CN111393983A (zh) * 2020-04-13 2020-07-10 浙江大学 一种荧光低表面能海洋防污涂料及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935179B4 (de) * 1999-07-27 2005-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photobiologisch aktive Beschichtungsmasse und ihre Verwendung
WO2008156691A1 (en) * 2007-06-19 2008-12-24 Duke University Anitcoagulants as antifouling agents
CN109852225A (zh) * 2019-01-28 2019-06-07 浙江大学 一种兼具低表面能和水解自抛光功能的有机硅聚氨酯防污材料及其应用
CN110669188B (zh) * 2019-10-21 2020-10-13 南京林业大学 一种可通过紫外光自修复的水性聚氨酯涂层及其制备方法
CN111187565B (zh) * 2020-01-06 2021-10-26 浙江大学衢州研究院 一种聚硅氧烷防污漆连接涂料及其制备方法
CN111471154B (zh) * 2020-05-11 2022-05-10 中国科学院深圳先进技术研究院 一种光或热引发的自修复弹性体及其制备方法和应用
CN113150594B (zh) * 2021-01-29 2022-06-21 浙江大学衢州研究院 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153856A (zh) * 2011-02-24 2011-08-17 中山大学 一种光致可逆自修复聚氨酯薄膜及其制备和修复方法
CN111393983A (zh) * 2020-04-13 2020-07-10 浙江大学 一种荧光低表面能海洋防污涂料及其制备方法

Also Published As

Publication number Publication date
WO2022160853A1 (zh) 2022-08-04
CN113150594A (zh) 2021-07-23
US20230212419A1 (en) 2023-07-06

Similar Documents

Publication Publication Date Title
CN113150594B (zh) 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
CN111393983B (zh) 一种荧光低表面能海洋防污涂料及其制备方法
CN111138974B (zh) 超支化硅烷改性聚氨酯复合聚硅氧烷防污涂料及制备方法
CN111187565B (zh) 一种聚硅氧烷防污漆连接涂料及其制备方法
CN102432802A (zh) 生物降解型防污涂料用树脂、合成方法，含该树脂的防污涂料组合物
CN113150673A (zh) 一种侧链硅氧烷功能化聚氨酯涂料及其制备方法与应用
CN107163224B (zh) 一种生物降解型高分子海洋防污材料及其制备与应用
JPH10508639A (ja) 防汚ペイント組成物
CN112794975A (zh) 一种用于海洋无毒防污的有机硅改性聚脲及其制备方法
CN113105817B (zh) 一种侧链多巴胺功能化聚氨酯涂料及其制备方法与应用
CN112625599A (zh) 一种快速自修复超韧有机硅改性聚脲硫脲防污涂层及其制备方法
WO1998042452A1 (en) Hydrophobic films
CN108659190B (zh) 一种自抛光型低表面能聚氨酯及其制备方法和应用
CN115851110B (zh) 一种基于香豆素的光响应长效超润滑防污涂料的制备方法
DE60017913T2 (de) Selbstpolierende anwuchsverhindernde anstrichfarbe für wasserfahrzeuge-enthaltend blockierte säurefunktionelle copolymere und fasern
CN1772828A (zh) 海洋网箱网衣防污涂料
CN116240728B (zh) 水性仿生环保防污涂料及其制备方法和应用
CN114292589B (zh) 一种低模量渔网用防污漆的制备方法
CN111117477A (zh) 一种嵌入紫外led灯珠的高透紫外防污涂层系统及其制备方法
CN115851097B (zh) 一种多孔液体注入的光响应超润滑防污涂料的制备方法
Yi et al. Synthesis and characterization of degradable polyurethane based on poly (ether ester) polyols (PPG-2000 and ε-caprolactone/lactic acid) for marine antifouling
CN117210107B (zh) 自抛光耐腐蚀抗菌自修复低表面能的涂层材料的制备方法
CN113105816A (zh) 一种侧链环氧功能化聚氨酯涂料及其制备方法与应用
CN116285643A (zh) 一种高强度超韧有机硅改性聚氨酯防污涂层及其制备方法
CN114479582A (zh) 一种临海油气管道静态环境下用无铜防污涂料及制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant