WO2021232236A1 - 一种离子型硅凝胶防污涂料及其制备方法 - Google Patents

一种离子型硅凝胶防污涂料及其制备方法 Download PDF

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WO2021232236A1
WO2021232236A1 PCT/CN2020/091044 CN2020091044W WO2021232236A1 WO 2021232236 A1 WO2021232236 A1 WO 2021232236A1 CN 2020091044 W CN2020091044 W CN 2020091044W WO 2021232236 A1 WO2021232236 A1 WO 2021232236A1
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parts
component
silicone gel
solvent
ionic silicone
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PCT/CN2020/091044
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English (en)
French (fr)
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李春光
刘轶龙
陈珊珊
杨名亮
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厦门双瑞船舶涂料有限公司
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Priority to PCT/CN2020/091044 priority Critical patent/WO2021232236A1/zh
Priority to CN202080005838.3A priority patent/CN113056532A/zh
Publication of WO2021232236A1 publication Critical patent/WO2021232236A1/zh

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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D5/1687—Use of special additives

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  • the invention relates to the technical field of chemical materials, in particular to an ionic silicone gel antifouling paint and a preparation method thereof.
  • the biological adhesion on the surface of ship hulls and marine structures is a complex and dynamic process involving multiple factors. It is difficult for a single anti-fouling strategy to achieve effective and long-lasting anti-fouling effects, just like the multiple anti-fouling effects of marine biological skins.
  • the synergy of the mechanism and anti-fouling should also consider a variety of coordinated anti-fouling strategies to achieve the desired anti-fouling effect.
  • WO2013107827A1 discloses the advantages of fouling-releasing antifouling coatings, which are friendly to the marine environment and can minimize ship fuel consumption. However, this coating is preferably applied to ships with a speed of 15 knots, while in slower-moving ships or On a stationary surface, the application effect is not ideal, and it is easily contaminated by dirt.
  • EP3617278A discloses that pure silicon-based fouling coatings are difficult to form a surface with low biological pollution in a highly polluted static marine environment.
  • the present invention provides an ionic silicone gel antifouling paint, which includes component A and component B Component
  • the first component includes double polyethylene glycol-terminated polydimethylsiloxane (BPEG-PDMS), hydroxyl-terminated polydimethylsiloxane (PDMS), pigments and solvents;
  • the second group It includes bis[3-(triethoxysilyl)propyl]amine (BTSA), zwitterionic acrylic monomer and solvent.
  • the first component includes the following parts by weight of raw materials: the di-polyethylene glycol-terminated polydimethylsiloxane is 5-25 parts, and the hydroxyl-terminated polydimethylsiloxane is 5-25 parts.
  • the amount of methylsiloxane (PDMS) is 40-60 parts, the pigment is 2-4 parts, and the solvent is 5-10 parts.
  • the pigment is selected from one or more of titanium white, iron yellow, iron red and carbon black.
  • BPEG-PDMS bis-polyethylene glycol-terminated polydimethylsiloxane
  • b is 15-25, and c is 15-20.
  • PDMS hydroxyl-terminated polydimethylsiloxane
  • the a is 150-250.
  • the preparation method of the first component is: stirring and dispersing the di-polyethylene glycol-terminated polydimethylsiloxane, the solvent and the pigment, and the stirring and dispersing is preferably carried out at 2000 rpm. Disperse for 40 minutes.
  • the second component includes the following parts by weight of raw materials: the second component includes the following parts by weight of raw materials: the bis[3-(triethoxysilyl)propyl] Amine (BTSA) is 10-30 parts, the zwitterionic acrylic monomer is 1-10 parts, and the solvent is 5-10 parts.
  • BTSA bis[3-(triethoxysilyl)propyl] Amine
  • the zwitterionic acrylic monomer is [2-(methacryloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SBA) And one or two of 3-[[2-(acryloyloxy)ethyl]dimethylammonium]propionate.
  • the preparation method of the second component is: under the conditions of anhydrous, nitrogen atmosphere and 35°C, bis[3-(triethoxysilyl)propyl]amine (BTSA) ), the zwitterionic acrylic monomer and the solvent are ultrasonically dispersed, and the ultrasonic dispersion time is preferably 1 h.
  • BTSA bis[3-(triethoxysilyl)propyl]amine
  • the solvent is one of toluene, xylene, acetone and methyl isobutyl ketone.
  • the present invention also provides a preparation method of ionic silicone gel antifouling coating, including the following preparation methods of component A and component B:
  • the preparation method of the first component is as follows: stirring and dispersing the polydimethylsiloxane, the solvent and the pigment, which are capped with dipolyethylene glycol, and the stirring and dispersing is preferably carried out at a rotation speed of 2000 rpm for 40 minutes;
  • the preparation method of the second component is: under the conditions of anhydrous, nitrogen atmosphere and 35°C, bis[3-(triethoxysilyl)propyl]amine (BTSA), zwitterionic acrylic monomer and solvent Ultrasonic dispersion, the ultrasonic dispersion time is preferably 1h.
  • the first component includes the following parts by weight of raw materials: the di-polyethylene glycol-terminated polydimethylsiloxane is 5-25 parts, and the hydroxyl-terminated polydimethylsiloxane is 5-25 parts.
  • the amount of methylsiloxane (PDMS) is 40-60 parts, the pigment is 2-4 parts, and the solvent is 5-10 parts.
  • the first component includes the following parts by weight of raw materials: the di-polyethylene glycol-terminated polydimethylsiloxane is 5-25 parts, and the hydroxyl-terminated polydimethylsiloxane is 5-25 parts.
  • the amount of methylsiloxane (PDMS) is 40-60 parts, the pigment is 2-4 parts, and the solvent is 5-10 parts.
  • the pigment is selected from one or more of titanium white, iron yellow, iron red and carbon black.
  • BPEG-PDMS bis-polyethylene glycol-terminated polydimethylsiloxane
  • b is 15-25, and c is 15-20.
  • PDMS hydroxyl-terminated polydimethylsiloxane
  • the a is 150-250.
  • the second component includes the following parts by weight of raw materials: the second component includes the following parts by weight of raw materials: the bis[3-(triethoxysilyl)propyl] Amine (BTSA) is 10-30 parts, the zwitterionic acrylic monomer is 1-10 parts, and the solvent is 5-10 parts.
  • BTSA bis[3-(triethoxysilyl)propyl] Amine
  • the zwitterionic acrylic monomer is [2-(methacryloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide (SBA) And one or two of 3-[[2-(acryloyloxy)ethyl]dimethylammonium]propionate (CBA).
  • the solvent is one of toluene, xylene, acetone and methyl isobutyl ketone.
  • the ionic silicone gel antifouling paint and its preparation method provided by the present invention have the following advantages: bis[3-(triethoxysilyl)propyl]amine (BTSA) and Zwitterionic monomers react to produce zwitterionic silane coupling agents.
  • BTSA bis[3-(triethoxysilyl)propyl]amine
  • Zwitterionic monomers react to produce zwitterionic silane coupling agents.
  • tertiary amine type zwitterionic silane coupling agents can autocatalyze and react with BPEG-PDMS and PDMS; thereby repelling zwitterionic charges
  • the characteristics, the fouling and desorption characteristics of PDMS and the anti-protein characteristics of polyethylene glycol PEG are combined in an anti-fouling coating system to obtain a bionic structure surface coating, which can effectively prevent marine organisms from attaching in a highly polluted static marine environment.
  • Figure 1 is a schematic diagram of antifouling of an ionic silicone gel antifouling paint provided by the present invention
  • Fig. 2 is a bar graph of the test results of the diatom adhesion performance of an ionic silicone gel antifouling coating provided by the present invention.
  • the present invention also provides the following examples and comparative examples:
  • the b of the BPEG-PDMS is 15, c is 15; the a of PDMS is 150; the solvent in the first component is toluene; the pigment is titanium white; the zwitterionic acrylic monomer is SBA; the solvent in the second component is two Toluene
  • component A disperse BPEG-PDMS, PDMS, toluene and titanium dioxide at 2000 rpm for 40 minutes, and stir evenly;
  • the preparation method of the second component is: BTSA, SBA and xylene are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • the b of the BPEG-PDMS is 20 and c is 18; the a of PDMS is 200; the solvent in the first component is toluene; the pigment is iron yellow; the zwitterionic acrylic monomer is CBA; the solvent in the second component is two Toluene
  • component A disperse BPEG-PDMS, PDMS, toluene and iron yellow at 2000 rpm for 40 minutes and stir evenly;
  • component B is: BTSA, CBA and xylene are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • the b of the BPEG-PDMS is 22 and c is 18; the a of PDMS is 225; the solvent in the first component is toluene; the pigment is iron red; the zwitterionic acrylic monomer is SBA; the solvent in the second component is two Toluene
  • component A disperse BPEG-PDMS, PDMS, toluene and iron red at 2000 rpm for 40 minutes, and stir evenly;
  • the preparation method of the second component is: BTSA, SBA and xylene are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • the b of the BPEG-PDMS is 23 and c is 19; the a of PDMS is 240; the solvent in the first component is acetone; the pigment is carbon black; the zwitterionic acrylic monomer is CBA; the solvent in the second component is acetone ;
  • component A The preparation method of component A is: disperse BPEG-PDMS, PDMS, acetone and carbon black at 2000 rpm for 40 minutes, and stir evenly;
  • the preparation method of the second component is: BTSA, CBA and acetone are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • the b of the BPEG-PDMS is 17, c is 21; the a of PDMS is 190; the solvent in the first component is methyl isobutyl ketone; the pigment is iron red; the zwitterionic acrylic monomer is SBA; the second component is The solvent is acetone;
  • component A disperse BPEG-PDMS, PDMS, methyl isobutyl ketone and iron red at 2000 rpm for 40 minutes, and stir evenly;
  • the preparation method of the second component is: BTSA, SBA and acetone are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • the b of the BPEG-PDMS is 25 and c is 18; the a of PDMS is 240; the solvent in the first component is xylene; the pigment is iron red; the zwitterionic acrylic monomer is CBA; the solvent in the second component is Toluene
  • component A The preparation method of component A is: disperse BPEG-PDMS, PDMS, xylene and iron red at 2000 rpm for 40 minutes, and stir evenly;
  • component B is: BTSA, CBA and toluene are dispersed ultrasonically for 1 hour under the conditions of anhydrous, nitrogen atmosphere and 35°C.
  • Example 1 Example 2
  • Example 3 Example 4 Contact angle (°) 102 103 105
  • Test items Example 5
  • Example 6 Comparison ⁇ Contact angle (°) 104 107 109 ⁇
  • the prepared coating is hydrophobic.
  • Diatom adhesion test Navicula was used to conduct anti-diatom adhesion test on the coating.
  • the diatoms were cultured with F/2 medium under a 12:12 hour light-dark cycle at 25°C.
  • Add 3.0 mL of a diatom suspension with a concentration of 1.0*105 cells/mL to each well of a 24-well plate coated with a polymer-coated glass slide, and then incubate for 24 hours. Subsequently, the glass slide was gently washed with sterilized and filtered artificial seawater to remove unattached diatoms. Observe with an optical microscope (Scope A1, Zeiss) and count 5 fields of view. Each PDMS-based coating is tested with 3 parallel samples to obtain the average value.
  • Example 1 Example 2
  • Example 3 Example 4 score 85
  • 86 91
  • Test items Example 5
  • Example 6 Comparison ⁇

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  • Engineering & Computer Science (AREA)
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Abstract

一种离子型硅凝胶防污涂料，包括甲组分和乙组分；甲组分包括双聚乙二醇封端的聚二甲基硅氧烷、羟基封端聚二甲基硅氧烷、颜料和溶剂；乙组分包括双[3-(三乙氧基硅)丙基]胺、两性离子丙烯酸单体和溶剂。该防污涂料的制备方法包括甲组分和乙组分的制备方法：甲组分的制备方法为：将双聚乙二醇封端的聚二甲基硅氧、溶剂和颜料进行搅拌分散；乙组分的制备方法为：在无水、氮气氛围和35℃条件下，将双[3-(三乙氧基硅)丙基]胺、两性离子丙烯酸单体和溶剂进行超声分散。

Description

一种离子型硅凝胶防污涂料及其制备方法 技术领域
本发明涉及化工材料技术领域，特别涉及一种离子型硅凝胶防污涂料及其制备方法。
背景技术
船体，海洋建筑物的表面的生物粘附是一个复杂的、动态的过程，涉及多种因素，单一防污策略很难达到有效、长效的防污效果，正如海洋生物表皮的多种防污机制的协同作用，防污也应该考虑多种协同的防污策略，以达到期望的防污效果。
近年来，随着人们对海洋环境保护的日益重视，无毒防污涂料的研究取得了一定的进展，含有无毒天然防污剂的涂料由于天然防污剂的难以获得，而无法大规模应用，由此，科研的方向开始朝向不含防污剂的生物污损释放型涂层。
WO2013107827A1公开了污损释放型防污涂料的优点，对海洋环境友好，可以最大限度的减少船舶燃料消耗，但是这种涂层优选应用在航速15节的船舶上，而在运动较慢的船舶或者静止的表面上，应用效果则不理想，容易受污垢污染。
而EP3617278A公开了纯硅基污损涂层在高污染静止海洋环境难以形成低生物污染的表面。
发明内容
为解决现有技术中在高污染静止海洋环境下不能有效防止海洋生物附着 以及防污涂料对环境不够友好的问题，本发明提供一种离子型硅凝胶防污涂料，包括甲组分和乙组分；
其中，所述甲组分包括双聚乙二醇封端的聚二甲基硅氧烷(BPEG-PDMS)、羟基封端聚二甲基硅氧烷(PDMS)、颜料和溶剂；所述乙组分包括双[3-(三乙氧基硅)丙基]胺(BTSA)、两性离子丙烯酸单体和溶剂。
在上述方案的基础上，进一步地，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷(PDMS)为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
在上述方案的基础上，进一步地，所述颜料选自钛白、铁黄、铁红和碳黑中的一种或多种。
在上述方案的基础上，进一步地，所述双聚乙二醇封端的聚二甲基硅氧烷(BPEG-PDMS)的结构式如下所示：
Figure PCTCN2020091044-appb-000001
其中，所述b为15～25，c为15～20。
在上述方案的基础上，进一步地，所述羟基封端聚二甲基硅氧烷(PDMS)的结构式如下所示：
Figure PCTCN2020091044-appb-000002
其中，所述a为150～250。
在上述方案的基础上，进一步地，所述甲组分的制备方法为：将双聚乙二醇封端的聚二甲基硅氧、溶剂和颜料进行搅拌分散，所述搅拌分散优选以2000rpm转速进行分散40min。
在上述方案的基础上，进一步地，所述乙组分包括以下重量份的原料：所述乙组分包括以下重量份的原料：所述双[3-(三乙氧基硅)丙基]胺(BTSA)为10～30份，所述两性离子丙烯酸单体为1～10份，所述溶剂为5～10份。
在上述方案的基础上，进一步地，所述两性离子丙烯酸单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵(SBA)和3-[[2-(丙烯酰氧)乙基]二甲基铵]丙酸酯中的一种或两种。
在上述方案的基础上，进一步地，所述乙组分的制备方法为：在无水、氮气氛围和35℃条件下，将双[3-(三乙氧基硅)丙基]胺(BTSA)、两性离子丙烯酸单体和溶剂进行超声分散，所述超声分散的时间优选为1h。
在上述方案的基础上，进一步地，所述溶剂为甲苯、二甲苯、丙酮和甲基异丁基甲酮中的一种。
本发明还提供一种离子型硅凝胶防污涂料的制备方法，包括以下甲组分和乙组分的制备方法：
所述甲组分的制备方法为：将双聚乙二醇封端的聚二甲基硅氧、溶剂和颜料进行搅拌分散，所述搅拌分散优选以2000rpm转速进行分散40min；
所述乙组分的制备方法为：在无水、氮气氛围和35℃条件下，将双[3-(三乙氧基硅)丙基]胺(BTSA)、两性离子丙烯酸单体和溶剂进行超声分散，所述超声分散的时间优选为1h。
在上述方案的基础上，进一步地，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷(PDMS)为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
在上述方案的基础上，进一步地，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷(PDMS)为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
在上述方案的基础上，进一步地，所述颜料选自钛白、铁黄、铁红和碳黑中的一种或多种。
在上述方案的基础上，进一步地，所述双聚乙二醇封端的聚二甲基硅氧烷(BPEG-PDMS)的结构式如下所示：
Figure PCTCN2020091044-appb-000003
其中，所述b为15～25，c为15～20。
在上述方案的基础上，进一步地，所述羟基封端聚二甲基硅氧烷(PDMS)的结构式如下所示：
Figure PCTCN2020091044-appb-000004
其中，所述a为150～250。
在上述方案的基础上，进一步地，所述乙组分包括以下重量份的原料：所述乙组分包括以下重量份的原料：所述双[3-(三乙氧基硅)丙基]胺(BTSA)为10～30份，所述两性离子丙烯酸单体为1～10份，所述溶剂为5～10份。
在上述方案的基础上，进一步地，所述两性离子丙烯酸单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵(SBA)和3-[[2-(丙烯酰氧)乙基]二甲基铵]丙酸酯(CBA)中的一种或两种。
在上述方案的基础上，进一步地，所述溶剂为甲苯、二甲苯、丙酮和甲基异丁基甲酮中的一种。
本发明提供的一种离子型硅凝胶防污涂料及其制备方法，与现有技术相比，具有以下优点：采用双[3-(三乙氧基硅)丙基]胺(BTSA)与两性离子单体反应生成具有两性离子性的硅烷偶联剂，同时叔胺类型的两性离子性的硅烷 偶联剂能够很好的自催化与BPEG-PDMS、PDMS反应；从而将两性离子电荷的排斥特性、PDMS的污损脱附特性以及聚乙二醇PEG的抗蛋白特性，融合在一个防污涂层体系，得到仿生结构表面涂层，可以在高污染静止海洋环境下有效防止海洋生物附着。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明提供的一种离子型硅凝胶防污涂料的防污示意图；
图2为本发明提供的一种离子型硅凝胶防污涂料的硅藻粘附性能测试结果柱状图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明还提供如下所示实施例和对比例：
表1实施例1-3各组分表
Figure PCTCN2020091044-appb-000005
Figure PCTCN2020091044-appb-000006
表2实施例4-6各组分表
Figure PCTCN2020091044-appb-000007
实施例1
所述BPEG-PDMS的b为15，c为15；PDMS的a为150；甲组分中的溶剂为甲苯；颜料为钛白；两性离子丙烯酸单体为SBA；乙组分中的溶剂为二甲苯；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、甲苯和钛白，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、SBA和二甲苯，在无水、氮气氛围和35℃条件下，超声分散1小时。
实施例2
所述BPEG-PDMS的b为20，c为18；PDMS的a为200；甲组分中的溶剂为甲苯；颜料为铁黄；两性离子丙烯酸单体为CBA；乙组分中的溶剂为二甲苯；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、甲苯和铁黄，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、CBA和二甲苯，在无水、氮气氛围和35℃条件下，超声分散1小时。
实施例3
所述BPEG-PDMS的b为22，c为18；PDMS的a为225；甲组分中的溶剂为甲苯；颜料为铁红；两性离子丙烯酸单体为SBA；乙组分中的溶剂为二甲苯；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、甲苯和铁红，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、SBA和二甲苯，在无水、氮气氛围和35℃条件下，超声分散1小时。
实施例4
所述BPEG-PDMS的b为23，c为19；PDMS的a为240；甲组分中的溶剂 为丙酮；颜料为炭黑；两性离子丙烯酸单体为CBA；乙组分中的溶剂为丙酮；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、丙酮和炭黑，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、CBA和丙酮，在无水、氮气氛围和35℃条件下，超声分散1小时。
实施例5
所述BPEG-PDMS的b为17，c为21；PDMS的a为190；甲组分中的溶剂为甲基异丁基甲酮；颜料为铁红；两性离子丙烯酸单体为SBA；乙组分中的溶剂为丙酮；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、甲基异丁基甲酮和铁红，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、SBA和丙酮，在无水、氮气氛围和35℃条件下，超声分散1小时。
实施例6
所述BPEG-PDMS的b为25，c为18；PDMS的a为240；甲组分中的溶剂为二甲苯；颜料为铁红；两性离子丙烯酸单体为CBA；乙组分中的溶剂为甲苯；
并按照以下制备方法：
甲组分制备方法为：将BPEG-PDMS、PDMS、二甲苯和铁红，以2000rpm转速分散40分钟，搅拌均匀；
乙组分的制备方法为：将BTSA、CBA和甲苯，在无水、氮气氛围和35℃条件下，超声分散1小时。
对比例
采用市售的intersleek900型号的防污涂料；
上述的实施例按照甲：乙＝2:1(质量比)进行测试，并与对比例进行如下测试：
表3实施例和对比例涂层接触角测试结果
测试项目 实施例1 实施例2 实施例3 实施例4
接触角(°) 102 103 105 104
测试项目 实施例5 实施例6 对比例 \
接触角(°) 104 107 109 \
根据表3的接触角测试结果表明所制备的涂层有疏水性。
硅藻粘附实验：采用舟形藻对涂层进行抗硅藻粘附实验。硅藻用F/2培养基培养，条件为25℃下的12：12小时光照-黑暗循环。将3.0mL浓度为1.0*105cells/mL的硅藻悬浮液加到涂布有聚合物涂膜的玻璃片的24孔板的每一个孔中，随后培养24小时。随后，用已灭菌已过滤的人工海水轻轻冲玻璃片以除去未附着的硅藻。用光学显微镜(Scope A1,Zeiss)观察并取5个视野计数，每种PDMS基涂层均用3个平行样测试以得到平均值。
根据图2结果显示，可以得出具有两性离子和PEG-PDMS的硅凝胶具有良好的抗硅藻粘附性能。
对两性离子硅凝胶防污涂料实施例、对比例按照国家标准GB/T 5370-2007《防污漆样板浅海浸泡试验方法》进行检测，测试结果如下表所示：
表4离子型硅凝胶防污涂料防污结果(挂板4个月)
测试项目 实施例1 实施例2 实施例3 实施例4
评分 85 86 91 87
测试项目 实施例5 实施例6 对比例 \
评分 88 92 70 \
从上述数据，即表3，图2和表4的测试结果，可以看出本发明提供的离子型硅凝胶防污涂层的防污效果良好。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (19)

  1. 一种离子型硅凝胶防污涂料，其特征在于，包括甲组分和乙组分；
    其中，所述甲组分包括双聚乙二醇封端的聚二甲基硅氧烷、羟基封端聚二甲基硅氧烷、颜料和溶剂；所述乙组分包括双[3-(三乙氧基硅)丙基]胺、两性离子丙烯酸单体和溶剂。
  2. 根据权利要求1所述的离子型硅凝胶防污涂料，其特征在于，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
  3. 根据权利要求1或2所述的离子型硅凝胶防污涂料，其特征在于：所述颜料选自钛白、铁黄、铁红和碳黑中的一种或多种。
  4. 根据权利要求1或2所述的离子型硅凝胶防污涂料，其特征在于，所述双聚乙二醇封端的聚二甲基硅氧烷的结构式如下所示：
    Figure PCTCN2020091044-appb-100001
    其中，所述b为15～25，c为15～20。
  5. 根据权利要求1或2所述的离子型硅凝胶防污涂料，其特征在于，所述羟基封端聚二甲基硅氧烷的结构式如下所示：
    Figure PCTCN2020091044-appb-100002
    其中，所述a为150～250。
  6. 根据权利要求1～5任一项所述的离子型硅凝胶防污涂料，其特征在于，所述甲组分的制备方法为：将双聚乙二醇封端的聚二甲基硅氧、溶剂和颜料进行搅拌分散。
  7. 根据权利要求1所述的离子型硅凝胶防污涂料，其特征在于，所述乙组分包括以下重量份的原料：所述乙组分包括以下重量份的原料：所述双[3-(三乙氧基硅)丙基]胺为10～30份，所述两性离子丙烯酸单体为1～10份，所述溶剂为5～10份。
  8. 根据权利要求1或7所述的离子型硅凝胶防污涂料，其特征在于：所述两性离子丙烯酸单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵和3-[[2-(丙烯酰氧)乙基]二甲基铵]丙酸酯中的一种或两种。
  9. 根据权利要求1或7或8所述的离子型硅凝胶防污涂料，其特征在于，所述乙组分的制备方法为：在无水、氮气氛围和35℃条件下，将双[3-(三乙氧基硅)丙基]胺、两性离子丙烯酸单体和溶剂进行超声分散。
  10. 根据权利要求1～9任一项所述的离子型硅凝胶防污涂料，其特征在于，所述溶剂为甲苯、二甲苯、丙酮和甲基异丁基甲酮中的一种。
  11. 一种离子型硅凝胶防污涂料的制备方法，其特征在于，包括以下甲组分和乙组分的制备方法：
    所述甲组分的制备方法为：将双聚乙二醇封端的聚二甲基硅氧、溶剂和颜料进行搅拌分散；
    所述乙组分的制备方法为：在无水、氮气氛围和35℃条件下，将双[3-(三乙氧基硅)丙基]胺、两性离子丙烯酸单体和溶剂进行超声分散。
  12. 根据权利要求11所述的离子型硅凝胶防污涂料的制备方法，其特征在于，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
  13. 根据权利要求11或12所述的离子型硅凝胶防污涂料的制备方法，其特征在于，所述甲组分包括以下重量份的原料：所述双聚乙二醇封端的聚 二甲基硅氧为5～25份，所述羟基封端聚二甲基硅氧烷为40～60份，所述颜料为2～4份，所述溶剂为5～10份。
  14. 根据权利要求11-13任一项所述的离子型硅凝胶防污涂料的制备方法，其特征在于：所述颜料选自钛白、铁黄、铁红和碳黑中的一种或多种。
  15. 根据权利要求11-13任一项所述的离子型硅凝胶防污涂料的制备方法，其特征在于，所述双聚乙二醇封端的聚二甲基硅氧烷的结构式如下所示：
    Figure PCTCN2020091044-appb-100003
    其中，所述b为15～25，c为15～20。
  16. 根据权利要求11-13任一项所述的离子型硅凝胶防污涂料的制备方法，其特征在于，所述羟基封端聚二甲基硅氧烷的结构式如下所示：
    Figure PCTCN2020091044-appb-100004
    其中，所述a为150～250。
  17. 根据权利要求11所述的离子型硅凝胶防污涂料的制备方法，其特征在于，所述乙组分包括以下重量份的原料：所述乙组分包括以下重量份的原料：所述双[3-(三乙氧基硅)丙基]胺为10～30份，所述两性离子丙烯酸单体为1～10份，所述溶剂为5～10份。
  18. 根据权利要求11或17所述的离子型硅凝胶防污涂料的制备方法，其特征在于：所述两性离子丙烯酸单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵和3-[[2-(丙烯酰氧)乙基]二甲基铵]丙酸酯中的一种或两种。
  19. 根据权利要求11～18任一项所述的离子型硅凝胶防污涂料的制备方 法，其特征在于，所述溶剂为甲苯、二甲苯、丙酮和甲基异丁基甲酮中的一种。
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