WO2021036756A1 - 一种改性水性氟碳涂料及其制备方法 - Google Patents

一种改性水性氟碳涂料及其制备方法 Download PDF

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WO2021036756A1
WO2021036756A1 PCT/CN2020/107907 CN2020107907W WO2021036756A1 WO 2021036756 A1 WO2021036756 A1 WO 2021036756A1 CN 2020107907 W CN2020107907 W CN 2020107907W WO 2021036756 A1 WO2021036756 A1 WO 2021036756A1
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parts
water
modified water
emulsion
feve
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French (fr)
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叶秀芳
陈东初
崔兰州
周文雅
杨春艳
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佛山科学技术学院
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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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of coatings, in particular to a fluorocarbon coating and a preparation method thereof.
  • Fluorocarbon coatings with copolymers of fluoroolefin and alkyl vinyl ether or ester (FEVE) as the main film-forming material have outstanding advantages such as outstanding weather resistance, excellent comprehensive performance, and curing at room temperature, and are widely used in life and production .
  • FEVE fluorocarbon coatings is closely related to the level of fluorine content: the electronegativity of fluorine atoms is large, and the fluorocarbon bond has superior firmness and symmetry, which can endow fluorocarbon coatings with excellent comprehensive performance, and the general fluorine content The higher the value, the more obvious the performance advantage of fluorocarbon coatings.
  • the purpose of the present invention is to provide a modified water-based fluorocarbon coating and a preparation method thereof in view of the above-mentioned shortcomings of the prior art.
  • the technical scheme adopted by the present invention is: a modified water-based fluorocarbon coating, which comprises 40-60 parts of modified water-based FEVE fluorocarbon emulsion, 5-10 parts of sodium alginate aqueous solution, and 2 ⁇ 7 parts, 15 to 35 parts of pigments and fillers, 7 to 15 parts of additives, and 5 to 35 parts of solvents.
  • the modified water-based FEVE fluorocarbon emulsion consists of 25-40 parts of water-based FEVE emulsion and polymethacrylic acid based on the weight parts of raw materials. It is composed of 5 to 15 parts of 2-hydroxyethyl ester.
  • the water-based FEVE emulsion includes 20 to 45 parts by weight of the raw materials, monomers, 1 to 5 parts of initiators, 5 to 15 parts of emulsifiers, 5 to 25 parts of deionized water, and 5 parts by weight. ⁇ 15 servings.
  • the aqueous FEVE emulsion of the present invention is prepared by emulsion polymerization using specific compound monomers, and has good dispersibility with other raw material components in the coating system.
  • the monomers are composed of tetrafluoroethylene monomer, diethanol monoallyl ether monomer, cyclohexyl vinyl ether monomer and vinyl ether monomer in a molar ratio of 1 to 2: 0.5 ⁇ 1.5:0.5 ⁇ 1:0.5 ⁇ 2 composition.
  • the initiator is ammonium persulfate or potassium perphosphate.
  • the emulsifier is a polyol type nonionic emulsifier.
  • the co-solvent is dipropylene glycol butyl ether.
  • the volume ratio of the deionized water and dipropylene glycol butyl ether is 1:0.5-1.
  • the volume concentration of the sodium alginate aqueous solution is 0.5-1 g/100 mL.
  • the curing agent is a cyanate ester compound.
  • the pigment and filler are mixed with organically modified montmorillonite, rutile titanium dioxide and calcined kaolin in a mass ratio of 1:2 to 4:5 to 10.
  • the mesh number of the pigment and filler is 8000-10000 mesh, which is beneficial to improve the dispersibility of the pigment and filler in the resin system.
  • the auxiliary agent includes a dispersant, a thickener, a film-forming auxiliary, an anti-foaming and leveling agent, an anti-mold and anti-algae agent, and a pH adjusting agent.
  • the dispersant is a 0.2% volume concentration polyacrylamide aqueous solution dispersant, 0.5 to 3 parts by weight;
  • the defoaming and leveling agent is an organosilicon compound, 0.1 to 5 parts by weight;
  • the film-forming aid is lauryl ester, 1 to 5 parts by weight;
  • the thickener is a non-ionic associative polyurethane thickener, 0.5 to 2 parts by weight;
  • the anti-mold and algae-preventing agent is selected A mixture of one of 5-chloro-2-methyl-4isothiazolin-3-one or 2-methyl-4isothiazolin-3-one and a formaldehyde-releasing preservative, 0.05 to 1 part by weight
  • the pH adjuster is an ethanolamine neutralizer, 0.01 to 5 parts by weight.
  • the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:5-10.
  • a method for preparing the modified water-based fluorocarbon coating as described above which includes the following process steps:
  • the present invention innovatively introduces functional group-containing hydrophilic structural monomers from the perspective of molecular design, so as to achieve the purpose of improving the compatibility of the resin system with water and increasing the adhesion of the resin to form a film.
  • Specific modified water-based FEVE fluorocarbon emulsion, poly(2-hydroxyethyl methacrylate) and sodium alginate compound system to obtain water-based polyvinylidene fluoride coatings with comprehensive performance comparable to existing solvent-based fluorocarbon coatings.
  • the modified water-based fluorocarbon coating includes 40 parts of modified water-based FEVE fluorocarbon emulsion, 5 parts of sodium alginate aqueous solution with a volume concentration of 1g/100mL, 7 parts of cyanate ester compounds, pigments and fillers based on the weight of raw materials. 15 parts, 7-15 parts of additives and 35 parts of solvent, the modified water-based FEVE fluorocarbon emulsion is prepared by mixing 25 parts of water-based FEVE emulsion and 15 parts of 2-hydroxyethyl methacrylate based on raw material weight parts .
  • the water-based FEVE emulsion comprises 20 parts of monomers, 5 parts of ammonium persulfate or potassium perphosphate, 5 parts of polyol type nonionic emulsifier, 25 parts of deionized water and 5 parts of dipropylene glycol butyl ether based on the weight of raw materials.
  • the monomer is composed of tetrafluoroethylene monomer, diethanol monoallyl ether monomer, cyclohexyl vinyl ether monomer and vinyl ether monomer with a molar ratio of 1:1.5:0.5:2.
  • the pigment and filler are made by mixing organically modified montmorillonite, rutile titanium dioxide and calcined kaolin in a mass ratio of 1:2:10.
  • the auxiliary agent consists of 3 parts of 0.2% volume concentration of polyacrylamide aqueous solution dispersant, 0.5 part of non-ionic associative polyurethane thickener, 5 parts of lauryl ester film-forming auxiliary, 0.1 part of organic silicon compound, 5- It is composed of 1 part of anti-mildew and anti-algae agent mixed with chloro-2-methyl-4isothiazolin-3-one and formaldehyde-releasing preservative and 0.01 part of ethanolamine neutralizer.
  • the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:10.
  • the preparation method of the modified aqueous FEVE fluorocarbon emulsion is as follows:
  • step 3 Mix the aqueous FEVE emulsion obtained in step 2) with poly-2-hydroxyethyl methacrylate and stir uniformly to obtain the modified aqueous FEVE fluorocarbon emulsion of Example 1.
  • the modified water-based fluorocarbon coating includes 60 parts of a modified water-based FEVE fluorocarbon emulsion, 10 parts of sodium alginate aqueous solution with a volume concentration of 0.5g/100mL, 2 parts of cyanate ester compounds, and pigments. 35 parts of fillers, 7 parts of additives and 35 parts of solvents.
  • the modified water-based FEVE fluorocarbon emulsion is prepared by mixing 25 parts of water-based FEVE emulsion and 15 parts of 2-hydroxyethyl methacrylate based on raw material weight parts.
  • the water-based FEVE emulsion comprises 20 parts of monomers, 5 parts of ammonium persulfate or potassium perphosphate, 5 parts of polyol type nonionic emulsifier, 25 parts of deionized water and 5 parts of dipropylene glycol butyl ether based on the weight of raw materials.
  • the monomers are composed of tetrafluoroethylene monomer, diethanol monoallyl ether monomer, cyclohexyl vinyl ether monomer and vinyl ether monomer with a molar ratio of 2:0.5:1:0.5.
  • the pigment and filler are made by mixing organically modified montmorillonite, rutile titanium dioxide and calcined kaolin in a mass ratio of 1:4:5.
  • the auxiliary agent consists of 0.5 part of 0.2% volume concentration polyacrylamide aqueous solution dispersant, 2 parts of non-ionic associative polyurethane thickener, 1 part of lauryl ester film-forming auxiliary, 5 parts of organic silicon compound, 2- It is composed of 1 part of antifungal and algae prevention agent mixed with methyl-4isothiazolin-3-one and formaldehyde-releasing preservative and 0.01 part of ethanolamine neutralizer.
  • the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:5.
  • the preparation method of the modified aqueous FEVE fluorocarbon emulsion is as follows:
  • step 3 Mix the aqueous FEVE emulsion obtained in step 2) with poly-2-hydroxyethyl methacrylate and stir uniformly to obtain the modified aqueous FEVE fluorocarbon emulsion of Example 2.
  • the modified water-based fluorocarbon coating includes 50 parts of modified water-based FEVE fluorocarbon emulsion, 8 parts of sodium alginate aqueous solution with a volume concentration of 0.8g/100mL, 5 parts of cyanate ester compounds, and pigments. 20 parts of fillers, 10 parts of additives and 20 parts of solvents.
  • the modified water-based FEVE fluorocarbon emulsion is prepared by mixing 30 parts of water-based FEVE emulsion and 10 parts of 2-hydroxyethyl methacrylate based on raw material weight parts.
  • the water-based FEVE emulsion comprises 30 parts of monomers, 3 parts of ammonium persulfate or potassium perphosphate, 10 parts of polyol type non-ionic emulsifier, 15 parts of deionized water and 10 parts of dipropylene glycol butyl ether based on the weight of raw materials.
  • the monomer is composed of tetrafluoroethylene monomer, diethanol monoallyl ether monomer, cyclohexyl vinyl ether monomer and vinyl ether monomer with a molar ratio of 1:1:0.5:1.
  • the pigment and filler are mixed by organically modified montmorillonite, rutile titanium dioxide and calcined kaolin in a mass ratio of 1:3:8.
  • the auxiliary agent consists of 2 parts of 0.2% volume concentration polyacrylamide aqueous solution dispersant, 1 part of non-ionic associative polyurethane thickener, 3 parts of lauryl ester film-forming auxiliary, 3 parts of organic silicon compound, 5- It is composed of 0.5 part of anti-mold and algae-preventing agent mixed with chloro-2-methyl-4isothiazolin-3-one and formaldehyde-releasing preservative and 2 parts of ethanolamine neutralizer.
  • the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:8.
  • the preparation method of the modified aqueous FEVE fluorocarbon emulsion is as follows:
  • the modified water-based fluorocarbon coating includes 55 parts of modified water-based FEVE fluorocarbon emulsion, 8 parts of sodium alginate aqueous solution with a volume concentration of 0.8g/100mL, 5 parts of cyanate ester compounds, and pigments based on the weight of raw materials. 30 parts of fillers, 12 parts of additives and 15 parts of solvents.
  • the modified water-based FEVE fluorocarbon emulsion is prepared by mixing 35 parts of water-based FEVE emulsion and 8 parts of 2-hydroxyethyl methacrylate based on raw material weight parts.
  • the water-based FEVE emulsion comprises 28 parts of monomers, 2 parts of ammonium persulfate or potassium perphosphate, 12 parts of polyol-type non-ionic emulsifier, 20 parts of deionized water and 12 parts of dipropylene glycol butyl ether based on the weight of raw materials.
  • the monomers are composed of tetrafluoroethylene monomer, diethanol monoallyl ether monomer, cyclohexyl vinyl ether monomer and vinyl ether monomer with a molar ratio of 2:0.5:0.5:0.5.
  • the pigment and filler are mixed by organically modified montmorillonite, rutile titanium dioxide and calcined kaolin in a mass ratio of 1:4:10.
  • the auxiliary agent consists of 2.5 parts of polyacrylamide aqueous solution dispersant with 0.2% volume concentration, 1.5 parts of non-ionic associative polyurethane thickener, 3 parts of lauryl ester film-forming auxiliary, 0.5 parts of organic silicon compound, 2- It is composed of 4 parts of anti-mold and algae-preventing agent mixed with methyl-4isothiazolin-3-one and formaldehyde-releasing preservative and 4 parts of ethanolamine neutralizer.
  • the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:10.
  • the preparation method of the modified aqueous FEVE fluorocarbon emulsion is as follows:
  • step 3 Mix the aqueous FEVE emulsion obtained in step 2) with poly-2-hydroxyethyl methacrylate and stir uniformly to obtain the modified aqueous FEVE fluorocarbon emulsion of Example 4.
  • the modified water-based fluorocarbon coating products prepared in Examples 1 to 4 were tested for performance, and Solvay PVDF solvent-based coating fluorocarbon coating (product model 5000HG) was selected as a comparative example.
  • the test results are shown in Table 1 below. .

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Abstract

一种改性水性氟碳涂料，其按原料重量份计包括改性水性FEVE氟碳乳液40～60份、海藻酸钠水溶液5～10份、固化剂2～7份、颜填料15～35份、助剂7～15份和溶剂5～35份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液25～40份和聚甲基丙烯酸2-羟乙酯5～15份组成。创新地从分子设计的角度出发，引入含官能团的亲水结构单体，达到改善树脂体系与水的相容性和增加树脂成膜附着力的目的，并设置特定的水性FEVE氟碳乳液、聚甲基丙烯酸2-羟乙酯和海藻酸钠复配体系，综合性能媲美现有溶剂型氟碳涂料。

Description

一种改性水性氟碳涂料及其制备方法 技术领域
本发明涉及涂料领域，特别涉及一种氟碳涂料及其制备方法。
背景技术
以氟烯烃与烷基乙烯基醚或酯的共聚物(FEVE)为主要成膜物的氟碳涂料具有耐候性突出、综合性能优异、可常温固化等突出优点，在生活和生产中被广泛应用。一般FEVE氟碳涂料的性能与其含氟量的高低密切相关：氟原子的电负性大，氟碳键具有优越的牢固性和对称性，可赋予氟碳涂料优异的综合性能，一般含氟量越高，氟碳涂料的性能优势越明显。然而，氟原子的高电负性同时赋予了氟树脂低表面张力的特性，使得其呈强疏水性，氟碳树脂基体对颜填料的润湿性较差，与助剂的相容性也有一定的限制。因此，目前市场上的FEVE液体涂料几乎都是溶剂型产品，主要存在污染环境、浪费能源，高成本等问题，目前欧洲已明确禁止喷涂溶剂型液体氟碳，因此，FEVE的水性化是FEVE液体涂料的必然出路。
发明内容
本发明的目的在于针对上述现有技术的不足，提供一种改性水性氟碳涂料及其制备方法。
本发明所采取的技术方案是：一种改性水性氟碳涂料，其按原料重量份计包括改性水性FEVE氟碳乳液40～60份、海藻酸钠水溶液5～10份、固化剂2～7份、颜填料15～35份、助剂7～15份和溶剂5～35份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液25～40份和聚甲基丙烯酸2-羟乙酯5～15份组成。
作为上述方案的进一步改进，所述水性FEVE乳液按原料重量份计包括单体20～45份、引发剂1～5份、乳化剂5～15份、去离子水5～25份和助溶剂5～15份。具体地，本发明的水性FEVE乳液采用特定复配的单体通过乳液聚合法制备所得，其与涂料体系中的其它原料组分之间有良好的分散性。
作为上述方案的进一步改进，所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为1～2:0.5～1.5:0.5～1:0.5～2组成。所述引发剂为过硫酸铵或过磷酸钾。所述乳化剂为多元醇型的非离子型乳化剂。所述助溶剂为二丙二醇丁醚。所述去离子水和二丙二醇丁醚的体积比为1:0.5～1。
作为上述方案的进一步改进，所述海藻酸钠水溶液的体积浓度为0.5～1g/100mL。
作为上述方案的进一步改进，所述固化剂为氰酸酯类化合物。
作为上述方案的进一步改进，所述颜填料由有机改性蒙脱土、金红石型钛白粉和煅烧高岭土按质量比为1:2～4:5～10混合而成。具体地，所述颜填料的目数为8000～10000目，其有利于提高颜填料在树脂体系中的分散性。
作为上述方案的进一步改进，所述助剂包括分散剂、增稠剂、成膜助剂、消泡流平剂、防霉防藻剂和pH调节剂。具体地，所述分散剂为0.2％体积浓度的聚丙烯酰胺水溶液分散剂，以重量计0.5～3份；所述消泡流平剂为有机硅化合物，以重量计0.1～5份；所述成膜助剂为十二醇酯，以重量计1～5份；所述增稠剂为非离子缔合型聚氨酯增稠剂，以重量计0.5～2份；所述防霉防藻剂选用5-氯-2-甲基-4异噻唑啉-3-酮或2-甲基-4异噻唑啉-3-酮其中一种与释放甲醛型防腐剂的混合物，以重量计0.05～1份；所述pH调节剂为乙醇胺类中和剂，以重量计0.01～5份。
作为上述方案的进一步改进，所述溶剂由聚乙二醇400和水按体积比为1:5～10混合而成。
一种如上所述的改性水性氟碳涂料的制备方法，其包括如下工艺步骤：
1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1000～1500rpm的速度搅拌8～15min，再以2000～3000rpm的速度搅拌20～30min，得白色漆浆；
2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于1500～2000rpm速度下搅拌20～30min，加入pH调节剂，调节pH＝8～9，加入增稠剂，以1500～2000rpm的速度搅拌10～15min，再加入防霉防藻剂，经研磨，得改性水性氟碳涂料成品。
本发明的有益效果是：本发明创新地从分子设计的角度出发，引入含官能团的亲水结构单体，达到改善树脂体系与水的相容性和增加树脂成膜附着力的目的，并设置特定的改性水性FEVE氟碳乳液、聚甲基丙烯酸2-羟乙酯和海藻酸钠复配体系，从而获得综合性能媲美现有溶剂型氟碳涂料的水性聚偏二氟乙烯涂料。
具体实施方式
下面结合实施例对本发明进行具体描述，以便于所属技术领域的人员对本发明的理解。有必要在此特别指出的是，实施例只是用于对本发明做进一步说明，不能理解为对本发明保护范围的限制，所属领域技术熟练人员，根据上述发明内容对本发明作出的非本质性的改进和调整，应仍属于本发明的保护范围。同时下述所提及的原料未详细说明的，均为市售产品；未详细提及的工艺步骤或制备方法为均为本领域技术人员所知晓的工艺步骤或制备方法。
实施例1
本实施例中改性水性氟碳涂料按原料重量份计包括改性水性FEVE氟碳乳液40份、体积 浓度为1g/100mL的海藻酸钠水溶液5份、氰酸酯类化合物7份、颜填料15份、助剂7～15份和溶剂35份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液25份和聚甲基丙烯酸2-羟乙酯15份混合制备而成。所述水性FEVE乳液按原料重量份计包括单体20份、过硫酸铵或过磷酸钾5份、多元醇型的非离子型乳化剂5份、去离子水25份和二丙二醇丁醚5份。其中所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为1:1.5:0.5:2组成。所述颜填料由有机改性蒙脱土、金红石型钛白粉和煅烧高岭土按质量比为1:2:10混合而成。所述助剂由0.2％体积浓度的聚丙烯酰胺水溶液分散剂3份、非离子缔合型聚氨酯增稠剂0.5份、十二醇酯成膜助剂5份、有机硅化合物0.1份、5-氯-2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂的混合而成的防霉防藻剂1份和乙醇胺类中和剂0.01份组成。所述溶剂由聚乙二醇400和水按体积比为1:10混合而成。
制备方法：
1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1500rpm的速度搅拌8min，再以3000rpm的速度搅拌20min，得白色漆浆；
2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于2000rpm速度下搅拌20min，加入pH调节剂，调节pH＝9，加入增稠剂，以1500rpm的速度搅拌15min，再加入防霉防藻剂，经研磨，得实施例1改性水性氟碳涂料成品。
其中所述改性水性FEVE氟碳乳液的制备方法如下：
1)室温下将纯化的二乙醇单烯丙基醚单体、环己基乙烯基醚单体、乙烯基醚单体、乳化剂OP-15混合，真空氮气气氛中搅拌分散30min；
2)加入去离子水、二丙二醇丁醚、过硫酸铵引发剂，继续搅拌分散，再加入乳化剂OP-15和四氟乙烯单体，搅拌升温至70℃并保温反应20h，得水性FEVE乳液；
3)将步骤2)所得水性FEVE乳液与聚甲基丙烯酸2-羟乙酯混合搅拌均匀，得实施例1改性水性FEVE氟碳乳液。
实施例2
本实施例中改性水性氟碳涂料按原料重量份计包括改性水性FEVE氟碳乳液60份、体积浓度为0.5g/100mL的海藻酸钠水溶液10份、氰酸酯类化合物2份、颜填料35份、助剂7份和溶剂35份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液25份和聚甲基丙烯酸2-羟乙酯15份混合制备而成。所述水性FEVE乳液按原料重量份计包括单体20份、过硫酸铵或过磷酸钾5份、多元醇型的非离子型乳化剂5份、去离子水25份和二丙二醇丁醚5份。其中所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为2:0.5:1:0.5组成。所述颜填料由有机改性蒙脱土、金红石型钛白粉 和煅烧高岭土按质量比为1:4:5混合而成。所述助剂由0.2％体积浓度的聚丙烯酰胺水溶液分散剂0.5份、非离子缔合型聚氨酯增稠剂2份、十二醇酯成膜助剂1份、有机硅化合物5份、2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂的混合而成的防霉防藻剂1份和乙醇胺类中和剂0.01份组成。所述溶剂由聚乙二醇400和水按体积比为1:5混合而成。
制备方法：
1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1000rpm的速度搅拌15min，再以2000rpm的速度搅拌30min，得白色漆浆；
2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于1500rpm速度下搅拌30min，加入pH调节剂，调节pH＝8，加入增稠剂，以2000rpm的速度搅拌10min，再加入防霉防藻剂，经研磨，得实施例2改性水性氟碳涂料成品。
其中所述改性水性FEVE氟碳乳液的制备方法如下：
1)室温下将纯化的二乙醇单烯丙基醚单体、环己基乙烯基醚单体、乙烯基醚单体、乳化剂OP-15混合，真空氮气气氛中搅拌分散30min；
2)加入去离子水、二丙二醇丁醚、过硫酸铵引发剂，继续搅拌分散，再加入乳化剂OP-15和四氟乙烯单体，搅拌升温至70℃并保温反应20h，得水性FEVE乳液；
3)将步骤2)所得水性FEVE乳液与聚甲基丙烯酸2-羟乙酯混合搅拌均匀，得实施例2改性水性FEVE氟碳乳液。
实施例3
本实施例中改性水性氟碳涂料按原料重量份计包括改性水性FEVE氟碳乳液50份、体积浓度为0.8g/100mL的海藻酸钠水溶液8份、氰酸酯类化合物5份、颜填料20份、助剂10份和溶剂20份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液30份和聚甲基丙烯酸2-羟乙酯10份混合制备而成。所述水性FEVE乳液按原料重量份计包括单体30份、过硫酸铵或过磷酸钾3份、多元醇型的非离子型乳化剂10份、去离子水15份和二丙二醇丁醚10份。其中所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为1:1:0.5:1组成。所述颜填料由有机改性蒙脱土、金红石型钛白粉和煅烧高岭土按质量比为1:3:8混合而成。所述助剂由0.2％体积浓度的聚丙烯酰胺水溶液分散剂2份、非离子缔合型聚氨酯增稠剂1份、十二醇酯成膜助剂3份、有机硅化合物3份、5-氯-2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂的混合而成的防霉防藻剂0.5份和乙醇胺类中和剂2份组成。所述溶剂由聚乙二醇400和水按体积比为1:8混合而成。
制备方法：
1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1500rpm的速 度搅拌10min，再以2500rpm的速度搅拌25min，得白色漆浆；
2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于2000rpm速度下搅拌25min，加入pH调节剂，调节pH＝9，加入增稠剂，以2000rpm的速度搅拌12min，再加入防霉防藻剂，经研磨，得实施例3改性水性氟碳涂料成品。
其中所述改性水性FEVE氟碳乳液的制备方法如下：
1)室温下将纯化的二乙醇单烯丙基醚单体、环己基乙烯基醚单体、乙烯基醚单体、乳化剂OP-15混合，真空氮气气氛中搅拌分散30min；
2)加入去离子水、二丙二醇丁醚、过硫酸铵引发剂，继续搅拌分散，再加入乳化剂OP-15和四氟乙烯单体，搅拌升温至70℃并保温反应20h，得水性FEVE乳液；
3)将步骤2)所得水性FEVE乳液与聚甲基丙烯酸2-羟乙酯混合搅拌均匀，得实施例3改性水性FEVE氟碳乳液。
实施例4
本实施例中改性水性氟碳涂料按原料重量份计包括改性水性FEVE氟碳乳液55份、体积浓度为0.8g/100mL的海藻酸钠水溶液8份、氰酸酯类化合物5份、颜填料30份、助剂12份和溶剂15份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液35份和聚甲基丙烯酸2-羟乙酯8份混合制备而成。所述水性FEVE乳液按原料重量份计包括单体28份、过硫酸铵或过磷酸钾2份、多元醇型的非离子型乳化剂12份、去离子水20份和二丙二醇丁醚12份。其中所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为2:0.5:0.5:0.5组成。所述颜填料由有机改性蒙脱土、金红石型钛白粉和煅烧高岭土按质量比为1:4:10混合而成。所述助剂由0.2％体积浓度的聚丙烯酰胺水溶液分散剂2.5份、非离子缔合型聚氨酯增稠剂1.5份、十二醇酯成膜助剂3份、有机硅化合物0.5份、2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂的混合而成的防霉防藻剂4份和乙醇胺类中和剂4份组成。所述溶剂由聚乙二醇400和水按体积比为1:10混合而成。
制备方法：
1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1500rpm的速度搅拌8min，再以3000rpm的速度搅拌20min，得白色漆浆；
2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于1500rpm速度下搅拌20min，加入pH调节剂，调节pH＝9，加入增稠剂，以1500rpm的速度搅拌10min，再加入防霉防藻剂，经研磨，得实施例4改性水性氟碳涂料成品。
其中所述改性水性FEVE氟碳乳液的制备方法如下：
1)室温下将纯化的二乙醇单烯丙基醚单体、环己基乙烯基醚单体、乙烯基醚单体、乳 化剂OP-15混合，真空氮气气氛中搅拌分散30min；
2)加入去离子水、二丙二醇丁醚、过硫酸铵引发剂，继续搅拌分散，再加入乳化剂OP-15和四氟乙烯单体，搅拌升温至70℃并保温反应20h，得水性FEVE乳液；
3)将步骤2)所得水性FEVE乳液与聚甲基丙烯酸2-羟乙酯混合搅拌均匀，得实施例4改性水性FEVE氟碳乳液。
实施例5：性能检测数据
将实施例1～4制备得的改性水性氟碳涂料成品分别进行性能检测，并选用美国苏威PVDF溶剂型涂料氟碳涂料(产品型号为5000HG)作为对比例其检测结果如下表1所示。
表1实施例与对比例各项性能检测结果
Figure PCTCN2020107907-appb-000001
上述实施例为本发明的优选实施例，凡与本发明类似的工艺及所作的等效变化，均应属于本发明的保护范畴。

Claims (9)

  1. 一种改性水性氟碳涂料，其特征在于：按原料重量份计包括改性水性FEVE氟碳乳液40～60份、海藻酸钠水溶液5～10份、固化剂2～7份、颜填料15～35份、助剂7～15份和溶剂5～35份，所述改性水性FEVE氟碳乳液按原料重量份计由水性FEVE乳液25～40份和聚甲基丙烯酸2-羟乙酯5～15份组成。
  2. 根据权利要求1所述的一种改性水性氟碳涂料，其特征在于：所述水性FEVE乳液按原料重量份计包括单体20～45份、引发剂1～5份、乳化剂5～15份、去离子水5～25份和助溶剂5～15份。
  3. 根据权利要求2所述的一种改性水性氟碳涂料，其特征在于：所述单体由四氟乙烯单体、二乙醇单烯丙基醚单体、环己基乙烯基醚单体和乙烯基醚单体按摩尔比为1～2:0.5～1.5:0.5～1:0.5～2组成。
  4. 根据权利要求1述的一种改性水性氟碳涂料，其特征在于：所述海藻酸钠水溶液的体积浓度为0.5～1g/100mL。
  5. 根据权利要求1述的一种改性水性氟碳涂料，其特征在于：所述固化剂为氰酸酯类化合物。
  6. 根据权利要求1述的一种改性水性氟碳涂料，其特征在于：所述颜填料由有机改性蒙脱土、金红石型钛白粉和煅烧高岭土按质量比为1:2～4:5～10混合而成。
  7. 根据权利要求1所述的一种改性水性氟碳涂料，其特征在于：所述助剂包括分散剂、增稠剂、成膜助剂、消泡流平剂、防霉防藻剂和pH调节剂。
  8. 根据权利要求1所述的一种改性水性氟碳涂料，其特征在于：所述溶剂由聚乙二醇400和水按体积比为1:5～10混合而成。
  9. 一种如权利要求1～8任一项所述的改性水性氟碳涂料的制备方法，其特征在于包括如下工艺步骤：
    1)将颜填料、固化剂、分散剂、成膜助剂、消泡流平剂和溶剂混合，以1000～1500rpm的速度搅拌8～15min，再以2000～3000rpm的速度搅拌20～30min，得白色漆浆；
    2)将白色漆浆与改性水性FEVE氟碳乳液和海藻酸钠水溶液混合，于1500～2000rpm速度下搅拌20～30min，加入pH调节剂，调节pH＝8～9，加入增稠剂，以1500～2000rpm的速度搅拌10～15min，再加入防霉防藻剂，经研磨，得改性水性氟碳涂料成品。
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CN109181457A (zh) * 2018-08-08 2019-01-11 佛山科学技术学院 一种改性水性pvdf涂料及制备方法
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CN110591472A (zh) * 2019-08-26 2019-12-20 佛山科学技术学院 一种改性水性氟碳涂料及其制备方法

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