WO2021036754A1 - 一种改性聚偏二氟乙烯氟碳涂料及其制备方法 - Google Patents

一种改性聚偏二氟乙烯氟碳涂料及其制备方法 Download PDF

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WO2021036754A1
WO2021036754A1 PCT/CN2020/107905 CN2020107905W WO2021036754A1 WO 2021036754 A1 WO2021036754 A1 WO 2021036754A1 CN 2020107905 W CN2020107905 W CN 2020107905W WO 2021036754 A1 WO2021036754 A1 WO 2021036754A1
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polyvinylidene fluoride
parts
modified polyvinylidene
modified
fluorocarbon coating
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English (en)
French (fr)
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叶秀芳
陈东初
廖玉婷
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佛山科学技术学院
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    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • 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
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the invention relates to the field of coatings, in particular to a polyvinylidene fluoride fluorocarbon coating and a preparation method thereof.
  • Fluorine resin refers to a polymer compound containing fluorine atoms on the carbon atoms of the main chain or side chain
  • PVDF polyvinylidene fluoride resin
  • the fluorocarbon bond formed by the most electronegative fluorine has excellent firmness and symmetry, which makes the polyvinylidene fluoride fluorocarbon coating have excellent properties, such as chemical corrosion resistance, oxidation resistance, high mechanical strength and toughness, and excellent It has a wide range of applications such as weather resistance.
  • the traditional polyvinylidene fluoride fluorocarbon coatings are mostly organic solvent-based coatings and powder coatings.
  • Organic solvent-based polyvinylidene fluoride fluorocarbon coatings will volatilize VOC during the preparation process and curing process, and the environmental protection performance is poor;
  • Polyvinylidene fluoride fluorocarbon coatings have disadvantages such as harsh curing temperature conditions and difficult construction, which limit the practical application of polyvinylidene fluoride fluorocarbon coatings.
  • Water-based fluorocarbon coatings made with water as a medium respond to the development policy of low-VOC or even VOC-free environmentally friendly coatings. They are not only suitable for market development and the upgrading of the coating industry, but also respond to people's desire for "green coatings".
  • Due to the strong electronegativity of the fluorine atoms the interaction between the fluorine atoms makes the fluorine atoms distributed in a spiral on the CC chain, which makes the gap energy between the two carbon atoms that are easily attacked on the main chain of the molecule. It is completely filled to form a highly three-dimensional shielded structure, most of the destructive groups are difficult to enter, so that the polyvinylidene fluoride resin has outstanding weather resistance and excellent comprehensive performance.
  • the purpose of the present invention is to provide a modified polyvinylidene fluoride fluorocarbon coating and a method for preparing the same.
  • the technical scheme adopted by the present invention is: a modified polyvinylidene fluoride fluorocarbon coating, which includes a modified polyvinylidene fluoride resin dispersion, which includes 30 to 30 parts by weight of the raw material. 45 parts, 5-15 parts of modifier, 0.5-1.5 parts of initiator, 35-60 parts of solvent, the modifier is made of polyethylene glycol monomaleate and polyethylene glycol methacrylate by weight The part ratio is 1:0.5 ⁇ 1.5.
  • the present invention grafts a specific ratio of polyethylene glycol monomaleate and polyethylene glycol methacrylate onto the polyvinylidene fluoride molecular chain for modification, so that the polyvinylidene fluoride resin has Hydrophilic side bonds modify the resin matrix from the strong hydrophobicity of pure PVDF resin to amphiphilic modified fluorocarbon resin, so as to achieve a significant improvement in polyvinylidene fluoride resin while maintaining excellent stability of the resin The purpose of compatibility with water.
  • the ratio of polyethylene glycol monomaleate to polyethylene glycol methacrylate is particularly important for the overall performance of the modified polyvinylidene fluoride resin coating, and it is only in the appropriate ratio range. Only in order to ensure that the modified polyvinylidene fluoride resin has good mechanical properties after film formation in the later stage, it has good water compatibility.
  • the initiator in step 2) is mixed with cuprous chloride and N-nitroso diisobutylamine in a mass ratio of 1:2.5 to 3.5.
  • cuprous chloride has a catalytic effect
  • a composite initiation system composed of a specific mass ratio of cuprous chloride and N-nitrosodiisobutylamine is beneficial to promote the polymerization reaction of the polyvinylidene fluoride resin and the modifier.
  • the solvent in step 5) is made by mixing 1,1,3-trimethylcyclohexenone and NMP in a volume ratio of 1:1 to 2. Specifically, the specific composition of the solvent reduces the amount of toxic organic solvents used while maximizing the solubility of the polyvinylidene fluoride resin.
  • the preparation method of the modified polyvinylidene fluoride resin dispersion liquid includes the following steps:
  • the mass ratio of the modified polyvinylidene fluoride copolymer to the solvent in step 5) is 1:0.5 to 1.5. Specifically, when the mass ratio of the modified polyvinylidene fluoride copolymer to the solvent is within an appropriate range, the modified polyvinylidene fluoride copolymer has good solubility in the fluorocarbon coating composition system. performance.
  • the modified polyvinylidene fluoride fluorocarbon coating includes 40 to 70 parts of modified polyvinylidene fluoride resin dispersion, 2 to 7 parts of curing agent, and 10 to 10 parts of pigments and fillers based on the weight of raw materials. 35 parts, 5-15 parts of auxiliary agent, 5-20 parts of co-solvent, 5-25 parts of deionized water.
  • the curing agent is a cyanate compound, such as selected from isophorone diisocyanate trimer (HDI) or isophorone diisocyanate (IPDI).
  • a cyanate compound such as selected from isophorone diisocyanate trimer (HDI) or isophorone diisocyanate (IPDI).
  • the pigment and filler are selected from at least one of organically modified montmorillonite, rutile titanium dioxide, and ultrafine mica powder.
  • the auxiliary agent includes a wetting and dispersing agent, a film-forming auxiliary agent, a leveling agent, an anti-mold and anti-algae agent, an antifoaming agent and a pH adjusting agent.
  • the wetting and dispersing agent is a polyurethane polymer compound such as BYK-163, which is 2-7 parts by weight; the film-forming aid is lauryl ester, which is 1-5 parts by weight;
  • the leveling agent is a fluorine-modified acrylic leveling agent, which is 1 to 5 parts by weight;
  • the anti-mold preservative is an isothiazolinone compound, such as CIT(5-chloro-2methyl-4isothiazoline- 3 ketone) and at least one of MIT (2-methyl-4-isothiazolin-3-one), 0.5 to 2 parts by weight;
  • the defoaming agent is a silicone or mineral oil defoaming agent, 0.1-2 parts by weight, ethanolamine is selected as the pH adjuster, and 0-7 parts by weight.
  • the co-solvent is at least one of dipropylene glycol methyl ether and dipropylene glycol butyl ether.
  • the volume ratio of dipropylene glycol methyl ether and dipropylene glycol butyl ether is 1:0.5 ⁇ 1.5.
  • a method for preparing the modified polyvinylidene fluoride fluorocarbon coating as described above which includes the following process steps:
  • the present invention innovatively starts from the molecular design point of view, selects polyethylene glycol monomaleate and polyethylene glycol methacrylate as modifiers, and adopts atom transfer radical polymerization method Obtain a polyethylene glycol monomaleate and polyethylene glycol methacrylate graft-modified polyvinylidene fluoride resin dispersion, make the polyvinylidene fluoride resin have hydrophilic side bonds, and the resin
  • the matrix is modified from the strong hydrophobicity of pure PVDF resin to amphiphilic modified fluorocarbon resin, and the modified polyvinylidene fluoride resin dispersion is used as the main film-forming material to obtain comprehensive performance comparable to existing solvent-based fluorine Water-based modified polyvinylidene fluoride fluorocarbon coating of carbon coating.
  • the raw material components of the modified polyvinylidene fluoride resin dispersion liquid include 30 parts of polyvinylidene fluoride resin, 10 parts of modifier, 1 part of initiator, and 35 parts of solvent based on the weight of the raw material.
  • the modifier is made by mixing polyethylene glycol monomaleate and polyethylene glycol methacrylate in a weight ratio of 1:1.5.
  • the initiator is made of cuprous chloride and N-nitroso Isobutylamine is mixed at a mass ratio of 1:2.5, and the solvent is mixed with 1,1,3-trimethylcyclohexenone and NMP at a volume ratio of 1:2.
  • the raw material components of the modified polyvinylidene fluoride fluorocarbon coating include 70 parts of modified polyvinylidene fluoride resin dispersion, 3 parts of curing agent, 15 parts of pigments and fillers, and 15 parts of auxiliary agents in terms of parts by weight of raw materials. , 10 parts of co-solvent, 20 parts of deionized water, wherein the curing agent is HDI, the pigment filler is composed of 5 parts of organically modified montmorillonite, 5 parts of rutile titanium dioxide and 5 parts of ultrafine mica powder.
  • the additives are 3 parts BYK-163 wetting and dispersing agent, 3 parts lauryl ester film-forming additives, 4 parts fluorine-modified acrylic leveling agent, 1 part MIT anti-mold preservative, 1 part silicone defoamer It is composed of 3 parts of ethanolamine pH regulator, and the co-solvent is composed of 5 parts of dipropylene glycol methyl ether and 5 parts of dipropylene glycol butyl ether.
  • the modified polyvinylidene fluoride copolymer is mixed with a solvent formed by mixing 1,1,3-trimethylcyclohexenone and N-methylpyrrolidone, mixing, stirring and dispersing uniformly to obtain examples 1 Modified polyvinylidene fluoride resin dispersion.
  • the raw material components of the modified polyvinylidene fluoride resin dispersion liquid include 30 parts of polyvinylidene fluoride resin, 10 parts of modifier, 1 part of initiator, and 35 parts of solvent based on the weight of the raw material.
  • the modifier is made by mixing polyethylene glycol monomaleate and polyethylene glycol methacrylate in a weight ratio of 1:0.5
  • the initiator is made of cuprous chloride and N-nitroso two Isobutylamine is mixed at a mass ratio of 1:3.5
  • the solvent is mixed with 1,1,3-trimethylcyclohexenone and NMP at a volume ratio of 1:1.5.
  • the raw material components of the modified polyvinylidene fluoride fluorocarbon coating include 60 parts of modified polyvinylidene fluoride resin dispersion, 7 parts of curing agent, 15 parts of pigments and fillers, and 15 parts of auxiliary agents in terms of parts by weight of raw materials.
  • the curing agent is HDI
  • the pigment filler is composed of 10 parts of organically modified montmorillonite and 5 parts of rutile titanium dioxide
  • the auxiliary agent is composed of 5 parts of BYK -163 wetting and dispersing agent, 3 parts lauryl ester film-forming additives, 2 parts fluorine-modified acrylic leveling agent, 1 part MIT anti-mold preservative, 1 part silicone defoamer and 3 parts ethanolamine pH adjuster It is composed of 5 parts of dipropylene glycol methyl ether and 10 parts of dipropylene glycol butyl ether.
  • the modified polyvinylidene fluoride copolymer is mixed with a solvent formed by mixing 1,1,3-trimethylcyclohexenone and N-methylpyrrolidone, mixing, stirring and dispersing uniformly to obtain examples 2 Modified polyvinylidene fluoride resin dispersion.
  • the raw material components of the modified polyvinylidene fluoride resin dispersion liquid include 45 parts of polyvinylidene fluoride resin, 5 parts of modifier, 1.5 parts of initiator, and 40 parts of solvent based on the weight parts of raw materials.
  • the modifier is made by mixing polyethylene glycol monomaleate and polyethylene glycol methacrylate at a weight ratio of 1:1
  • the initiator is made up of cuprous chloride and N-nitroso two Isobutylamine is mixed at a mass ratio of 1:3, and the solvent is mixed with 1,1,3-trimethylcyclohexenone and NMP at a volume ratio of 1:1.
  • the raw material components of the modified polyvinylidene fluoride fluorocarbon coating include 70 parts of modified polyvinylidene fluoride resin dispersion, 7 parts of curing agent, 17 parts of pigments and fillers, and 15 parts of auxiliary agents in terms of parts by weight of the raw materials.
  • the curing agent is CIT
  • the pigment filler is composed of 12 parts of organically modified montmorillonite and 5 parts of superfine mica powder
  • the auxiliary agent is composed of 4 parts of BYK -163 wetting and dispersing agent, 3 parts lauryl ester film-forming aids, 4 parts fluorine-modified acrylic leveling agent, 1 part MIT anti-mold preservative, 1 part silicone defoamer and 2 parts ethanolamine pH adjuster It is composed of 5 parts of dipropylene glycol methyl ether and 10 parts of dipropylene glycol butyl ether.
  • the modified polyvinylidene fluoride copolymer is mixed with a solvent formed by mixing 1,1,3-trimethylcyclohexenone and N-methylpyrrolidone, mixing, stirring and dispersing uniformly to obtain examples 3 Modified polyvinylidene fluoride resin dispersion.
  • the raw material components of the modified polyvinylidene fluoride resin dispersion liquid include 40 parts of polyvinylidene fluoride resin, 15 parts of modifier, 0.5 parts of initiator, and 60 parts of solvent based on the weight parts of raw materials.
  • the modifier is made by mixing polyethylene glycol monomaleate and polyethylene glycol methacrylate at a weight ratio of 1:1
  • the initiator is made up of cuprous chloride and N-nitroso two Isobutylamine is mixed at a mass ratio of 1:3, and the solvent is mixed with 1,1,3-trimethylcyclohexenone and NMP at a volume ratio of 1:1.
  • the raw material components of the modified polyvinylidene fluoride fluorocarbon coating include 40 parts of modified polyvinylidene fluoride resin dispersion, 2 parts of curing agent, 12 parts of pigments and fillers, and 6 parts of auxiliary agents in terms of parts by weight of the raw materials.
  • co-solvent is composed of 2 parts of dipropylene glycol methyl ether and 3 parts of dipropylene glycol butyl ether.
  • the modified polyvinylidene fluoride copolymer is mixed with a solvent formed by mixing 1,1,3-trimethylcyclohexenone and N-methylpyrrolidone, mixing, stirring and dispersing uniformly to obtain examples 4 Modified polyvinylidene fluoride resin dispersion.
  • the raw material components of the modified polyvinylidene fluoride resin dispersion liquid include 45 parts of polyvinylidene fluoride resin, 5 parts of modifier, 1 part of initiator, and 50 parts of solvent in terms of raw material weight parts.
  • the modifier is made by mixing polyethylene glycol monomaleate and polyethylene glycol methacrylate in a weight ratio of 1:1.2, and the initiator is made of cuprous chloride and N-nitroso Isobutylamine is mixed at a mass ratio of 1:2.8, and the solvent is mixed with 1,1,3-trimethylcyclohexenone and NMP at a volume ratio of 1:2.
  • the raw material components of the modified polyvinylidene fluoride fluorocarbon coating include 50 parts of modified polyvinylidene fluoride resin dispersion, 5 parts of curing agent, 35 parts of pigments and fillers, and 12 parts of auxiliary agents in terms of parts by weight of the raw materials.
  • the curing agent is HDI
  • the pigment filler is composed of 10 parts of organically modified montmorillonite, 15 parts of rutile titanium dioxide and 10 parts of ultrafine mica powder
  • the additives are 3 parts BYK-163 wetting and dispersing agent, 3 parts lauryl ester film-forming additives, 2 parts fluorine-modified acrylic leveling agent, 2 parts MIT anti-mold preservative, 1 part silicone defoamer And 1 part of ethanolamine pH regulator
  • the co-solvent is composed of 7 parts of dipropylene glycol methyl ether and 8 parts of dipropylene glycol butyl ether.
  • the modified polyvinylidene fluoride copolymer is mixed with a solvent formed by mixing 1,1,3-trimethylcyclohexenone and N-methylpyrrolidone, mixing, stirring and dispersing uniformly to obtain examples 5 Modified polyvinylidene fluoride resin dispersion.
  • the modified polyvinylidene fluoride fluorocarbon coating products prepared in Examples 1 to 5 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 as follows Table 1 shows.

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Abstract

本发明公开了一种改性聚偏二氟乙烯氟碳涂料，其包括改性聚偏二氟乙烯树脂分散液，其按原料重量份计包括聚偏二氟乙烯树脂30～45份、改性剂5～15份、引发剂0.5～1.5份、溶剂35～60份，所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:0.5～1.5组成。本发明创新地从分子设计的角度出发，选用聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯为改性剂，使聚偏二氟乙烯树脂具有亲水性的侧键，将树脂基体由纯PVDF树脂的强疏水性改性为具有两亲性的改性氟碳树脂，并以改性聚偏二氟乙烯树脂分散液作为主要成膜物，获得综合性能媲美现有溶剂型氟碳涂料的水性化改性聚偏二氟乙烯氟碳涂料。

Description

一种改性聚偏二氟乙烯氟碳涂料及其制备方法 技术领域
本发明涉及涂料领域，特别涉及一种聚偏二氟乙烯氟碳涂料及其制备方法。
背景技术
氟树脂是指主链或侧链的碳原子上含有氟原子的高分子化合物，聚偏二氟乙烯树脂(PVDF)是制备聚偏二氟乙烯氟碳涂料的树脂基体。电负性最大的氟形成的氟碳键具有优越的牢固性和对称性，使得聚偏二氟乙烯氟碳涂料具有优良的性能，如耐化学腐蚀、耐氧化、高机械强度和韧性、卓越的耐气候性等，其应用领域广泛。然而传统的聚偏二氟乙烯氟碳涂料多为有机溶剂类涂料和粉末涂料，有机溶剂型的聚偏二氟乙烯氟碳涂料在制备过程和固化过程中会挥发VOC，环保性能较差；粉末聚偏二氟乙烯氟碳涂料存在固化温条件苛刻，施工难度大等缺点，这些都限制了聚偏二氟乙烯氟碳涂料的实际应用。
以水为介质制成的水性氟碳涂料响应了低VOC甚至无VOC的环保涂料的发展方针，不仅适合市场发展及涂料行业的升级，更是响应了人们对“绿色涂料”的渴望。然而，由于氟原子的电负性强，氟原子之间的相互作用力使得氟原子在C-C链上呈螺旋状分布，其使分子主链上容易被进攻的两个碳原子之间的空隙能被完全填满，从而形成了高度立体屏蔽的结构，大部分破坏性基团难以进入，使得聚偏二氟乙烯树脂具有突出的耐候性和优异的综合性能。但也正是由于聚偏二氟乙烯树脂上F原子的高电负性，而导致了聚偏二氟乙烯F树脂的表面张力低、亲水性差。所以，聚偏二氟乙烯树脂的水性化改性成为了聚偏二氟乙烯氟碳涂料水性化开发的关键技术难题。
发明内容
本发明的目的在于上述现有技术的不足，提供一种改性聚偏二氟乙烯氟碳涂料及其制备方法。
本发明所采取的技术方案是：一种改性聚偏二氟乙烯氟碳涂料，其包括改性聚偏二氟乙烯树脂分散液，其按原料重量份计包括聚偏二氟乙烯树脂30～45份、改性剂5～15份、引发剂0.5～1.5份、溶剂35～60份，所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:0.5～1.5组成。
具体地，本发明将特定比例的聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯接枝到聚偏二氟乙烯分子链上进行改性，使聚偏二氟乙烯树脂具有亲水性的侧键，将树脂基体由纯PVDF 树脂的强疏水性改性为具有两亲性的改性氟碳树脂，从而达到在保持树脂优异稳定性的同时显著改善聚偏二氟乙烯树脂与水的相容性的目的。在研究过程中发现，聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯的比例对改性聚偏二氟乙烯树脂涂膜的综合性能尤为重要，其只有在合适的比例范围内才能保证改性聚偏二氟乙烯树脂在后期成膜后具有良好的力学性能的基础上具有良好的水相容性。
作为上述方案的进一步改进，步骤2)中所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:2.5～3.5混合而成。具体地，氯化亚铜具有催化作用，其与N-亚硝基二异丁胺按特定的质量比构成的复合型引发体系有利于促进聚偏二氟乙烯树脂与改性剂的聚合反应。
作为上述方案的进一步改进，步骤5)中所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:1～2混合而成。具体地，溶剂的特定组成在尽可能提高聚偏二氟乙烯树脂溶解性能的前提下降低了毒害有机溶剂的使用量。
作为上述方案的进一步改进，所述改性聚偏二氟乙烯树脂分散液的制备方法包括如下步骤：
1)将聚偏二氟乙烯树脂粉末充分溶解到NMP溶液中，加入改性剂并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌分散均匀；
3)加热至85～95℃，搅拌反应15～30h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、过滤、真空抽滤，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与溶剂混合搅拌分散均匀，得到改性聚偏二氟乙烯树脂分散液。
作为上述方案的进一步改进，步骤5)中所述改性聚偏二氟乙烯共聚物与溶剂的质量比为1:0.5～1.5。具体地，当改性聚偏二氟乙烯共聚物与溶剂的质量比在合适的范围内时，所述改性聚偏二氟乙烯共聚物在该氟碳涂料组合物体系中才具有良好的溶解性能。
作为上述方案的进一步改进，该改性聚偏二氟乙烯氟碳涂料按原料重量份计包括改性聚偏二氟乙烯树脂分散液40～70份、固化剂2～7份、颜填料10～35份、助剂5～15份、助溶剂5～20份、去离子水5～25份。
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，如选自异佛尔酮二异氰酸酯三聚体(HDI)或异佛尔酮二异氰酸酯(IPDI)。
作为上述方案的进一步改进，所述颜填料选自有机改性蒙脱土、金红石型钛白粉、超细云母粉中的至少一种。
作为上述方案的进一步改进，所述助剂包括润湿分散剂、成膜助剂、流平剂、防霉防藻剂、消泡剂和pH调节剂。具体地，所述润湿分散剂选用聚氨酯型高分子化合物如BYK-163，以重量计2～7份；所述成膜助剂为十二醇酯，以重量计1～5份；所述流平剂选用氟改性丙烯酸流平剂，以重量计1～5份；所述防霉防腐剂选用异噻唑啉酮类化合物，如CIT(5-氯-2甲基-4异噻唑啉-3酮)和MIT(2-甲基-4-异噻唑啉-3-酮)的至少一种，以重量计0.5～2份；所述消泡剂为有机硅或矿物油消泡剂，以重量计0.1～2份，所述pH调节剂选用乙醇胺，以重量计0～7份。
作为上述方案的进一步改进，所述助溶剂为二丙二醇甲醚和二丙二醇丁醚的至少一种，当选用其混合物时，所述二丙二醇甲醚和二丙二醇丁醚的体积比为1:0.5～1.5。
一种如上所述的改性聚偏二氟乙烯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、助剂、助溶剂和去离子水混合，以1500～2000rpm的速度搅拌8～15min，再以2500～3000rpm的速度搅拌10～25min，得白色漆浆；
2)将白色漆浆与改性聚偏二氟乙烯树脂分散液混合，于1500～2000rpm速度下搅拌15～25min，调节pH＝8～9，经研磨，得改性聚偏二氟乙烯氟碳涂料成品。
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，选用聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯为改性剂，采用原子转移自由基聚合法制备得到聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯接枝改性的聚偏二氟乙烯树脂分散液，使聚偏二氟乙烯树脂具有亲水性的侧键，将树脂基体由纯PVDF树脂的强疏水性改性为具有两亲性的改性氟碳树脂，并以改性聚偏二氟乙烯树脂分散液作为主要成膜物，获得综合性能媲美现有溶剂型氟碳涂料的水性化改性聚偏二氟乙烯氟碳涂料。
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
本实施例中改性聚偏二氟乙烯树脂分散液原料组分按原料重量份计包括聚偏二氟乙烯树脂30份、改性剂10份、引发剂1份、溶剂35份，其中所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:1.5混合而成，所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:2.5混合而成，所述溶剂由1,1,3-三甲基环己烯酮和NMP按体 积比为1:2混合而成。
本实施例中改性聚偏二氟乙烯氟碳涂料原料组分按原料重量份计包括改性聚偏二氟乙烯树脂分散液70份、固化剂3份、颜填料15份、助剂15份、助溶剂10份、去离子水20份，其中所述固化剂为HDI，所述颜填料由5份有机改性蒙脱土、5份金红石型钛白粉和5份超细云母粉组成，所述助剂由3份BYK-163润湿分散剂、3份十二醇酯成膜助剂、4份氟改性丙烯酸流平剂、1份MIT防霉防腐剂、1份有机硅消泡剂和3份乙醇胺pH调节剂组成，所述助溶剂由5份二丙二醇甲醚和5份二丙二醇丁醚组成。
改性聚偏二氟乙烯树脂分散液的制备方法：
1)按配方量将聚偏二氟乙烯树脂粉末充分溶解到50份的NMP溶液中，搅拌并加热体系至50℃充分溶解，冷却至室温，加入聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌30min分散均匀；
3)加热至90℃，搅拌反应20h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、经过滤、真空抽滤48h，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与由1,1,3-三甲基环己烯酮和N-甲基吡咯烷酮混合而成的溶剂混合搅拌分散均匀，得到实施例1改性聚偏二氟乙烯树脂分散液。
改性聚偏二氟乙烯氟碳涂料的制备方法：
1)按配方量将颜填料、固化剂、助剂、助溶剂和去离子水混合，以2000rpm的速度搅拌10min，再以2500rpm的速度搅拌15min，得白色漆浆；
2)将白色漆浆与配方量的改性聚偏二氟乙烯树脂分散液混合，于1500rpm速度下搅拌20min，调节pH＝8～9，经研磨，得实施例1改性聚偏二氟乙烯氟碳涂料成品。
实施例2
本实施例中改性聚偏二氟乙烯树脂分散液原料组分按原料重量份计包括聚偏二氟乙烯树脂30份、改性剂10份、引发剂1份、溶剂35份，其中所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:0.5混合而成，所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:3.5混合而成，所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:1.5混合而成。
本实施例中改性聚偏二氟乙烯氟碳涂料原料组分按原料重量份计包括改性聚偏二氟乙烯树脂分散液60份、固化剂7份、颜填料15份、助剂15份、助溶剂15份、去离子水25份，其中所述固化剂为HDI，所述颜填料由10份有机改性蒙脱土和5份金红石型钛白粉组成， 所述助剂由5份BYK-163润湿分散剂、3份十二醇酯成膜助剂、2份氟改性丙烯酸流平剂、1份MIT防霉防腐剂、1份有机硅消泡剂和3份乙醇胺pH调节剂组成，所述助溶剂由5份二丙二醇甲醚和10份二丙二醇丁醚组成。
改性聚偏二氟乙烯树脂分散液的制备方法：
1)按配方量将聚偏二氟乙烯树脂粉末充分溶解到50份的NMP溶液中，搅拌并加热体系至50℃充分溶解，冷却至室温，加入聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌30min分散均匀；
3)加热至85℃，搅拌反应30h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、经过滤、真空抽滤48h，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与由1,1,3-三甲基环己烯酮和N-甲基吡咯烷酮混合而成的溶剂混合搅拌分散均匀，得到实施例2改性聚偏二氟乙烯树脂分散液。
改性聚偏二氟乙烯氟碳涂料的制备方法：
1)按配方量将颜填料、固化剂、助剂、助溶剂和去离子水混合，以1500rpm的速度搅拌8min，再以3000rpm的速度搅拌10min，得白色漆浆；
2)将白色漆浆与配方量的改性聚偏二氟乙烯树脂分散液混合，于2000rpm速度下搅拌25min，调节pH＝8～9，经研磨，得实施例2改性聚偏二氟乙烯氟碳涂料成品。
实施例3
本实施例中改性聚偏二氟乙烯树脂分散液原料组分按原料重量份计包括聚偏二氟乙烯树脂45份、改性剂5份、引发剂1.5份、溶剂40份，其中所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:1混合而成，所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:3混合而成，所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:1混合而成。
本实施例中改性聚偏二氟乙烯氟碳涂料原料组分按原料重量份计包括改性聚偏二氟乙烯树脂分散液70份、固化剂7份、颜填料17份、助剂15份、助溶剂15份、去离子水25份，其中所述固化剂为CIT，所述颜填料由12份有机改性蒙脱土和5份超细云母粉组成，所述助剂由4份BYK-163润湿分散剂、3份十二醇酯成膜助剂、4份氟改性丙烯酸流平剂、1份MIT防霉防腐剂、1份有机硅消泡剂和2份乙醇胺pH调节剂组成，所述助溶剂由5份二丙二醇甲醚和10份二丙二醇丁醚组成。
改性聚偏二氟乙烯树脂分散液的制备方法：
1)按配方量将聚偏二氟乙烯树脂粉末充分溶解到50份的NMP溶液中，搅拌并加热体系至50℃充分溶解，冷却至室温，加入聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌30min分散均匀；
3)加热至95℃，搅拌反应15h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、经过滤、真空抽滤48h，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与由1,1,3-三甲基环己烯酮和N-甲基吡咯烷酮混合而成的溶剂混合搅拌分散均匀，得到实施例3改性聚偏二氟乙烯树脂分散液。
改性聚偏二氟乙烯氟碳涂料的制备方法：
1)按配方量将颜填料、固化剂、助剂、助溶剂和去离子水混合，以2000rpm的速度搅拌15min，再以2000rpm的速度搅拌25min，得白色漆浆；
2)将白色漆浆与配方量的改性聚偏二氟乙烯树脂分散液混合，于1500rpm速度下搅拌30min，调节pH＝8～9，经研磨，得实施例3改性聚偏二氟乙烯氟碳涂料成品。
实施例4
本实施例中改性聚偏二氟乙烯树脂分散液原料组分按原料重量份计包括聚偏二氟乙烯树脂40份、改性剂15份、引发剂0.5份、溶剂60份，其中所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:1混合而成，所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:3混合而成，所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:1混合而成。
本实施例中改性聚偏二氟乙烯氟碳涂料原料组分按原料重量份计包括改性聚偏二氟乙烯树脂分散液40份、固化剂2份、颜填料12份、助剂6份、助溶剂5份、去离子水10份，其中所述固化剂为CIT，所述颜填料由7份有机改性蒙脱土和5份超细云母粉组成，所述助剂由1份BYK-163润湿分散剂、1份十二醇酯成膜助剂、1份氟改性丙烯酸流平剂、1份MIT防霉防腐剂、1份有机硅消泡剂和1份乙醇胺pH调节剂组成，所述助溶剂由2份二丙二醇甲醚和3份二丙二醇丁醚组成。
改性聚偏二氟乙烯树脂分散液的制备方法：
1)按配方量将聚偏二氟乙烯树脂粉末充分溶解到30份的NMP溶液中，搅拌并加热体系至50℃充分溶解，冷却至室温，加入聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌30min分散均匀；
3)加热至85℃，搅拌反应20h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、经过滤、真空抽滤48h，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与由1,1,3-三甲基环己烯酮和N-甲基吡咯烷酮混合而成的溶剂混合搅拌分散均匀，得到实施例4改性聚偏二氟乙烯树脂分散液。
改性聚偏二氟乙烯氟碳涂料的制备方法：
1)按配方量将颜填料、固化剂、助剂、助溶剂和去离子水混合，以2000rpm的速度搅拌15min，再以2000rpm的速度搅拌25min，得白色漆浆；
2)将白色漆浆与配方量的改性聚偏二氟乙烯树脂分散液混合，于1500rpm速度下搅拌30min，调节pH＝8～9，经研磨，得实施例4改性聚偏二氟乙烯氟碳涂料成品。
实施例5
本实施例中改性聚偏二氟乙烯树脂分散液原料组分按原料重量份计包括聚偏二氟乙烯树脂45份、改性剂5份、引发剂1份、溶剂50份，其中所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:1.2混合而成，所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:2.8混合而成，所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:2混合而成。
本实施例中改性聚偏二氟乙烯氟碳涂料原料组分按原料重量份计包括改性聚偏二氟乙烯树脂分散液50份、固化剂5份、颜填料35份、助剂12份、助溶剂15份、去离子水25份，其中所述固化剂为HDI，所述颜填料由10份有机改性蒙脱土、15份金红石型的钛白粉和10份超细云母粉组成，所述助剂由3份BYK-163润湿分散剂、3份十二醇酯成膜助剂、2份氟改性丙烯酸流平剂、2份MIT防霉防腐剂、1份有机硅消泡剂和1份乙醇胺pH调节剂组成，所述助溶剂由7份二丙二醇甲醚和8份二丙二醇丁醚组成。
改性聚偏二氟乙烯树脂分散液的制备方法：
1)按配方量将聚偏二氟乙烯树脂粉末充分溶解到50份的NMP溶液中，搅拌并加热体系至50℃充分溶解，冷却至室温，加入聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯并混合分散均匀；
2)在氮气气氛中加入引发剂，于室温下搅拌30min分散均匀；
3)加热至90℃，搅拌反应30h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、经过滤、真空抽滤48h，得到改性聚偏二氟乙烯共聚物；
5)在冰水浴中将改性聚偏二氟乙烯共聚物与由1,1,3-三甲基环己烯酮和N-甲基吡咯烷 酮混合而成的溶剂混合搅拌分散均匀，得到实施例5改性聚偏二氟乙烯树脂分散液。
改性聚偏二氟乙烯氟碳涂料的制备方法：
1)按配方量将颜填料、固化剂、助剂、助溶剂和去离子水混合，以1500rpm的速度搅拌10min，再以3000rpm的速度搅拌20min，得白色漆浆；
2)将白色漆浆与配方量的改性聚偏二氟乙烯树脂分散液混合，于2000rpm速度下搅拌20min，调节pH＝8～9，经研磨，得实施例5改性聚偏二氟乙烯氟碳涂料成品。
实施例6：性能检测数据
将实施例1～5制备得的改性聚偏二氟乙烯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 PCTCN2020107905-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 (10)

  1. 一种改性聚偏二氟乙烯氟碳涂料，其特征在于：包括改性聚偏二氟乙烯树脂分散液，其按原料重量份计包括聚偏二氟乙烯树脂30～45份、改性剂5～15份、引发剂0.5～1.5份、溶剂35～60份，所述改性剂由聚乙二醇单马来酸酯和聚乙二醇甲基丙烯酸酯按重量份比例为1:0.5～1.5组成。
  2. 根据权利要求1所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：所述引发剂由氯化亚铜和N-亚硝基二异丁胺按质量比为1:2.5～3.5混合而成。
  3. 根据权利要求1所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：所述溶剂由1,1,3-三甲基环己烯酮和NMP按体积比为1:1～2混合而成。
  4. 根据权利要求1所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：所述改性聚偏二氟乙烯树脂分散液的制备方法包括如下步骤：
    1)将聚偏二氟乙烯树脂粉末充分溶解到NMP溶液中，加入改性剂并混合分散均匀；
    2)在氮气气氛中加入引发剂，于室温下搅拌分散均匀；
    3)加热至85～95℃，搅拌反应15～30h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
    4)将沉淀粗产物真空过滤成滤饼，用NMP溶液溶解，再用甲醇和石油醚的混合溶液沉淀、过滤、真空抽滤，得到改性聚偏二氟乙烯共聚物；
    5)在冰水浴中将改性聚偏二氟乙烯共聚物与溶剂混合搅拌分散均匀，得到改性聚偏二氟乙烯树脂分散液。
  5. 根据权利要求4所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：步骤5)中所述改性聚偏二氟乙烯共聚物与溶剂的质量比为1:0.5～1.5。
  6. 根据权利要求1～5任一项所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于按原料重量份计包括改性聚偏二氟乙烯树脂分散液40～70份、固化剂2～7份、颜填料10～35份、助剂5～15份、助溶剂5～20份、去离子水5～25份。
  7. 根据权利要求6所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：所述固化剂为氰酸酯类化合物。
  8. 根据权利要求6所述的一种改性聚偏二氟乙烯氟碳涂料，其特征在于：所述颜填料选自有机改性蒙脱土、金红石型钛白粉、超细云母粉中的至少一种。
  9. 一种如权利要求1～8任一项所述的改性聚偏二氟乙烯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、助剂、助溶剂和去离子水混合，以1500～2000rpm的速度搅拌8～15min，再以2500～3000rpm的速度搅拌10～25min，得白色漆浆；
    2)将白色漆浆与改性聚偏二氟乙烯树脂分散液混合，于1500～2000rpm速度下搅拌15～25min，调节pH＝8～9，经研磨，得改性聚偏二氟乙烯氟碳涂料成品。
  10. 根据权利要求9所述的一种改性聚偏二氟乙烯氟碳涂料的制备方法，其特征在于：所述助剂包括润湿分散剂、成膜助剂、流平剂、防霉防藻剂、消泡剂和pH调节剂。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162994A (ja) * 2003-12-05 2005-06-23 Daikin Ind Ltd 含フッ素水性分散組成物
CN101111525A (zh) * 2005-02-02 2008-01-23 株式会社吴羽 亲水性1,1-二氟乙烯树脂组合物和其制备方法
CN108314755A (zh) * 2018-03-06 2018-07-24 中山大学 一种环保型涂料印花粘合剂用乳液及其制备方法和应用
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
CN109621756A (zh) * 2019-01-28 2019-04-16 沈阳建筑大学 高通量抗污染的pvdf超滤膜的制备方法
CN110527430A (zh) * 2019-08-26 2019-12-03 佛山科学技术学院 一种改性聚偏二氟乙烯氟碳涂料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002211808A1 (en) * 2000-09-11 2002-03-26 Massachusetts Institute Of Technology Graft copolymers, methods for grafting hydrophilic chains onto hydrophobic polymers, and articles thereof
JP5189982B2 (ja) * 2006-08-14 2013-04-24 株式会社日本触媒 親水性グラフト重合体
US8741373B2 (en) * 2010-06-21 2014-06-03 Virun, Inc. Compositions containing non-polar compounds
CN102140181B (zh) * 2011-01-19 2013-04-17 天津工业大学 聚偏氟乙烯亲水改性膜及其制备方法
KR101923181B1 (ko) * 2017-04-28 2018-11-28 인하대학교 산학협력단 친수성 표면개질제를 이용한 소수성 고분자 메쉬의 표면개질 및 우레탄 코팅을 통한 표면처리 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162994A (ja) * 2003-12-05 2005-06-23 Daikin Ind Ltd 含フッ素水性分散組成物
CN101111525A (zh) * 2005-02-02 2008-01-23 株式会社吴羽 亲水性1,1-二氟乙烯树脂组合物和其制备方法
CN108314755A (zh) * 2018-03-06 2018-07-24 中山大学 一种环保型涂料印花粘合剂用乳液及其制备方法和应用
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
CN109621756A (zh) * 2019-01-28 2019-04-16 沈阳建筑大学 高通量抗污染的pvdf超滤膜的制备方法
CN110527430A (zh) * 2019-08-26 2019-12-03 佛山科学技术学院 一种改性聚偏二氟乙烯氟碳涂料及其制备方法

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