WO2021036757A1 - 一种水性聚偏二氟乙烯涂料及其制备方法 - Google Patents
一种水性聚偏二氟乙烯涂料及其制备方法 Download PDFInfo
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- polyvinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the invention relates to the field of coatings, in particular to a polyvinylidene fluoride coating and a preparation method thereof.
- PVDF polyvinylidene fluoride
- the comprehensive performance of the polyvinylidene fluoride (PVDF) coating film is very excellent.
- the use of more than 40 years in various harsh climates around the world proves that the PVDF fluorocarbon coating has the longest weather resistance.
- the polyvinylidene fluoride coating film also has outstanding chemical resistance, oxidation resistance, mechanical strength and toughness.
- the polyvinylidene fluoride coatings currently on the market are mostly solvent-based or powder-based.
- the main reason is that the electronegativity of the fluorine atoms is large, that is, the fluorine-carbon bond has superior firmness and symmetry, but it does not endow the polyvinylidene fluoride
- the excellent comprehensive performance of vinyl fluoride coatings also greatly reduces its surface tension and other characteristics, making the polyvinylidene fluoride coatings have strong hydrophobicity, and the polyvinylidene fluoride resin matrix itself has wettability and support for pigments and fillers.
- the compatibility of the agent is poor. Solvent-based polyvinylidene fluoride coatings will volatilize VOCs (volatile organic solvents) during the preparation and curing process, and have poor environmental performance.
- powder-based polyvinylidene fluoride coatings have harsh curing temperature conditions and difficult construction. Large shortcomings, these are all factors that restrict the wide application of polyvinylidene fluoride coatings. Therefore, the current polyvinylidene fluoride coating products on the market mainly have problems such as environmental pollution, energy waste, and high cost. At present, Europe has clearly banned the spraying of solvent-based polyvinylidene fluoride coatings. Therefore, the water-based polyvinylidene fluoride coating is an inevitable way for its further development and application.
- the purpose of the present invention is to provide a water-based polyvinylidene fluoride coating and a method for preparing the same.
- an aqueous polyvinylidene fluoride paint which comprises the following components in parts by weight of raw materials: 40-60 parts of modified polyvinylidene fluoride emulsion, 5-10 parts of sodium alginate aqueous solution Parts, 2 ⁇ 7 parts of curing agent, 15 ⁇ 35 parts of pigments and fillers, 7 ⁇ 15 parts of auxiliary agents, 5 ⁇ 35 parts of solvents.
- the modified polyvinylidene fluoride emulsion is treated with 2-hydroxyethyl methacrylate and oxygen Ethylene methacrylate graft modification.
- the structures of 2-hydroxyethyl methacrylate and oxyethylene methacrylate can be grafted to polyvinylidene fluoride via a free radical initiator, and compared with other modified monomers, methyl
- the hydroxyl group and ester group on 2-hydroxyethyl acrylate and the ether group and ester group on oxyethylene methacrylate are easier to form intermolecular hydrogen bonds with water, which can give polyvinylidene fluoride side chain good hydrophilicity , Thereby effectively improving the hydrophilic properties of the polyvinylidene fluoride body.
- sodium alginate As a natural polysaccharide, sodium alginate has a large number of hydrophilic hydroxyl groups, ester groups and ether groups on its surface, and its film-forming properties are strong. Compared with many hydrophilic substances, a certain amount of sodium alginate unexpectedly can further improve the compatibility of the fluorocarbon resin system with water and the film-forming performance at the same time.
- the modified polyvinylidene fluoride emulsion includes 10-15 parts of polyvinylidene fluoride resin powder, 5-10 parts of modifier, 0.5-1 part of initiator, 60 to 75 parts of solvent, wherein the modifier is composed of poly-2-hydroxyethyl methacrylate and polyoxyethylene methacrylate.
- the initiator is BPO or AIBN.
- the special selection of the initiator is beneficial to promote the polymerization reaction of the polyvinylidene fluoride resin and the modifier.
- the preparation method of the modified polyvinylidene fluoride emulsion includes the following steps:
- step 5) Add the modified polyvinylidene fluoride resin obtained in step 4) to the volume ratio of triethyl phosphate, 3,5,5-trimethyl-2-cyclohexenone and water to 1:2 ⁇ 3: In the mixed solution of 3-9, stir and disperse uniformly to obtain a modified polyvinylidene fluoride emulsion.
- the volume concentration of the sodium alginate aqueous solution is 0.5-1 g/100 mL.
- the curing agent is a cyanate compound, such as selected from 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate or biuret polyisocyanate.
- the pigment and filler are mixed with organically modified montmorillonite, titanium dioxide and calcined kaolin in a mass ratio of 1:2 to 4:5 to 10.
- 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 water-based polyvinylidene fluoride coating as described above which includes the following process steps:
- the beneficial effect of the present invention is: the present invention innovatively selects the modified polyvinylidene fluoride emulsion grafted with 2-hydroxyethyl methacrylate and oxyethylene methacrylate from the perspective of molecular design to make polyvinylidene fluoride emulsion
- the vinylidene fluoride resin has hydrophilic side bonds, and the resin matrix is modified from the strong hydrophobicity of pure PVDF resin to amphiphilic modified polyvinylidene fluoride resin, and modified polyvinylidene fluoride emulsion
- the main film-forming material supplemented by sodium alginate aqueous solution to further improve the water solubility of the resin system, a water-based polyvinylidene fluoride coating with comprehensive performance comparable to existing solvent-based fluorocarbon coatings can be obtained.
- the raw material components of the water-based polyvinylidene fluoride coating include 40 parts of modified polyvinylidene fluoride emulsion, 10 parts of sodium alginate aqueous solution, 2 parts of curing agent, 35 parts of pigments and fillers, and additives based on the weight of raw materials. 7 parts, 35 parts solvent, wherein the volume concentration of the sodium alginate aqueous solution is 0.5g/100mL, the curing agent is 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate, and the pigment
- the filler is made by mixing organically modified montmorillonite, titanium dioxide and calcined kaolin in a mass ratio of 1:2:5.
- the auxiliary agent is made up of 3 parts of 0.2% by volume polyacrylamide aqueous solution dispersant and 0.5 parts of non-ionic Associative polyurethane thickener, 5 parts lauryl ester film-forming aids, 0.1 parts silicone defoaming leveling agent, 1 part composed of 5-chloro-2-methyl-4isothiazolin-3-one and An anti-mold and anti-algae agent mixed with formaldehyde-releasing preservatives and 0.01 part of ethanolamine neutralizer, and the solvent is mixed with polyethylene glycol 400 and water in a volume ratio of 1:10.
- the raw material components of the modified polyvinylidene fluoride emulsion include 15 parts of polyvinylidene fluoride resin powder, 5 parts of modifier, 1 part of initiator, and 60 parts of solvent based on raw material weight parts. It is composed of 2-hydroxyethyl methacrylate and polyoxyethylene methacrylate, and the initiator is BPO.
- step 4) The modified polyvinylidene fluoride resin obtained in step 4) is added to the volume ratio of triethyl phosphate, 3,5,5-trimethyl-2-cyclohexenone and water as 1:3: In the mixed solution of 3, stir and disperse uniformly to obtain the modified polyvinylidene fluoride emulsion of Example 1.
- the raw material components of the water-based polyvinylidene fluoride coating include 60 parts of modified polyvinylidene fluoride emulsion, 5 parts of sodium alginate aqueous solution, 7 parts of curing agent, 15 parts of pigments and fillers, and auxiliary agents in terms of parts by weight of raw materials.
- the curing agent is biuret polyisocyanate
- the pigments and fillers are made of organically modified montmorillonite, titanium dioxide and calcined kaolin according to mass The ratio is 1:4:10
- the auxiliary agent is made up of 0.5 parts of 0.2% by volume polyacrylamide aqueous solution dispersant, 2 parts of non-ionic associative polyurethane thickener, and 1 part of lauryl ester to form a film.
- step 5) The modified polyvinylidene fluoride resin obtained in step 4) is added to the volume ratio of triethyl phosphate, 3,5,5-trimethyl-2-cyclohexenone and water as 1:2: The mixed solution of 9 was stirred and dispersed evenly to obtain the modified polyvinylidene fluoride emulsion of Example 2.
- the raw material components of the water-based polyvinylidene fluoride coating include 50 parts of modified polyvinylidene fluoride emulsion, 8 parts of sodium alginate aqueous solution, 5 parts of curing agent, 23 parts of pigments and fillers, and auxiliary agents in terms of parts by weight of raw materials. 10 parts, 20 parts solvent, the volume concentration of the sodium alginate aqueous solution is 0.8g/100mL, the curing agent is 3-isocyanatomethylene-3,5,5-trimethylcyclohexyl isocyanate, and the pigment
- the filler is made by mixing organically modified montmorillonite, titanium dioxide and calcined kaolin in a mass ratio of 1:3:8.
- the auxiliary agent is 1.5 parts of 0.2% volume concentration polyacrylamide aqueous solution dispersant, 1 part of non-ionic Associative polyurethane thickener, 3 parts lauryl ester film-forming aids, 3 parts silicone defoaming and leveling agents, 0.5 parts of 5-chloro-2-methyl-4isothiazolin-3-one and An anti-mold and anti-algae agent mixed with formaldehyde-releasing preservatives 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 raw material components of the modified polyvinylidene fluoride emulsion include 12 parts of polyvinylidene fluoride resin powder, 8 parts of modifier, 0.8 parts of initiator, and 70 parts of solvent in terms of parts by weight of raw materials. It is composed of 2-hydroxyethyl methacrylate and polyoxyethylene methacrylate, and the initiator is AIBN.
- step 5 The modified polyvinylidene fluoride resin obtained in step 4) is added to the volume ratio of triethyl phosphate, 3,5,5-trimethyl-2-cyclohexenone and water as 1:3: In the mixed solution of 5, stir and disperse uniformly to obtain the modified polyvinylidene fluoride emulsion of Example 3.
- the raw material components of the water-based polyvinylidene fluoride coating include 55 parts of modified polyvinylidene fluoride emulsion, 6 parts of sodium alginate aqueous solution, 4 parts of curing agent, 25 parts of pigments and fillers, and auxiliary agents in terms of parts by weight of raw materials. 12 parts, 30 parts solvent, in which the volume concentration of the sodium alginate aqueous solution is 1g/100mL, the curing agent is biuret polyisocyanate, and the pigments and fillers are made of organically modified montmorillonite, titanium dioxide and calcined kaolin according to mass The ratio is 1:4:8.
- the auxiliary agent is made up of 1 part of 0.2% volume concentration polyacrylamide aqueous solution dispersant, 1 part of non-ionic associative polyurethane thickener, and 4 parts of lauryl ester to form a film.
- the solvent is made by mixing polyethylene glycol 400 and water in a volume ratio of 1:8.
- the raw material components of the modified polyvinylidene fluoride emulsion include 10 parts of polyvinylidene fluoride resin powder, 8 parts of modifier, 1 part of initiator, and 60 parts of solvent in terms of parts by weight of the raw material. It is composed of 2-hydroxyethyl methacrylate and polyoxyethylene methacrylate, and the initiator is AIBN.
- the modified polyvinylidene fluoride resin obtained in step 4) is added to the volume ratio of triethyl phosphate, 3,5,5-trimethyl-2-cyclohexenone and water as 1:3: In the mixed solution of 5, stir and disperse uniformly to obtain the modified polyvinylidene fluoride emulsion of Example 4.
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Abstract
本发明公开了一种水性聚偏二氟乙烯涂料，其按原料重量份计包括如下组分：改性聚偏二氟乙烯乳液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、溶剂5～35份，所述改性聚偏二氟乙烯乳液经甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯接枝改性。本发明选用经甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯接枝的改性聚偏二氟乙烯乳液，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，并以改性聚偏二氟乙烯乳液作为主要成膜物，辅以海藻酸钠水溶液进一步提高树脂体系的水溶性，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。
Description
本发明涉及涂料领域，特别涉及一种聚偏二氟乙烯涂料及其制备方法。
聚偏二氟乙烯(PVDF)涂膜综合性能十分优异，在全球各地各种严酷气候环境中40多年的使用证明PVDF氟碳涂层具有最长久的耐候性能。此外，聚偏二氟乙烯涂膜还具有突出的耐化学腐蚀、耐氧化性、机械强度和韧性等。然而目前市场上的聚偏二氟乙烯涂料多为溶剂型或粉末型，其主要原因是氟原子的电负性大，即氟碳键具有优越的牢固性和对称性，但在赋予聚偏二氟乙烯涂料优异的综合性能的同时亦大大降低了其表面张力等特性，使得聚偏二氟乙烯涂料呈强疏水性，且聚偏二氟乙烯树脂基体本身对颜填料的润湿性和对助剂的相容性较差。而溶剂型的聚偏二氟乙烯涂料在制备过程和固化过程中会挥发VOC(挥发性有机溶剂)，环保性能较差，另外粉末型的聚偏二氟乙烯涂料存在固化温条件苛刻，施工难度大等缺点，这些都是制约聚偏二氟乙烯涂料广泛应用的因素。因此，目前市场上的聚偏二氟乙烯涂料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聚偏二氟乙烯涂料。所以，聚偏二氟乙烯涂料的水性化是其进一步发展应用的必然出路。
发明内容
本发明的目的在于上述现有技术的不足，提供一种水性聚偏二氟乙烯涂料及其制备方法。
本发明所采取的技术方案是：一种水性聚偏二氟乙烯涂料，其按原料重量份计包括如下组分：改性聚偏二氟乙烯乳液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、溶剂5～35份，所述改性聚偏二氟乙烯乳液经甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯接枝改性。
具体地，甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯的结构能通过自由基引发剂接枝到聚偏二氟乙烯基体上，且相较于其他的改性单体，甲基丙烯酸2-羟乙酯上的羟基与酯基和氧乙烯甲基丙烯酸酯上的醚基与酯基更易与水形成分子间的氢键，能赋予聚偏二氟乙烯侧链良好的亲水性，从而有效地改善聚偏二氟乙烯基体的亲水性能。而海藻酸钠作为天然多糖，其表面具有大量亲水性的羟基、酯基和醚基，其成膜性能强。相比众多的亲水性物质，特定量的海藻酸钠意外地能够进一步同时提高氟碳树脂体系与水的相容性及成膜性能。
作为上述方案的进一步改进，所述改性聚偏二氟乙烯乳液按原料重量份计包括聚偏二氟乙烯树脂粉末10～15份、改性剂5～10份、引发剂0.5～1份、溶剂60～75份，其中所述改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成。
作为上述方案的进一步改进，所述引发剂为BPO或AIBN。具体地，引发剂的特殊选用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，所述改性聚偏二氟乙烯乳液的制备方法包括如下步骤：
1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:2～3混合而成的溶剂中，加热至50～80℃，搅拌15～30min充分反应，加入纯化的改性剂，混合均匀；
2)在氮气气氛中加入引发剂，在70～80℃的氮气气氛中下继续搅拌反应6～8h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；
5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:2～3:3～9的混合溶液中，搅拌分散均匀，得到改性聚偏二氟乙烯乳液。
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，如选自3-异氰酸酯基亚甲基-3，5，5-三甲基环己基异氰酸酯或缩二脲多异氰酸酯。
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、钛白粉和煅烧高岭土按质量比为1:2～4:5～10混合而成。
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。
一种如上所述的水性聚偏二氟乙烯涂料的制备方法，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)将白色漆浆与改性聚偏二氟乙烯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，得水性聚偏二氟乙烯涂料成品。
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，选用经甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯接枝的改性聚偏二氟乙烯乳液，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聚偏二氟乙烯树脂，并以改性聚偏二氟乙烯乳液作为主要成膜物，辅以海藻酸钠水溶液进一步提高树脂体系的水溶性，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。
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
本实施例中水性聚偏二氟乙烯涂料原料组分按原料重量份计包括改性聚偏二氟乙烯乳液40份、海藻酸钠水溶液10份、固化剂2份、颜填料35份、助剂7份、溶剂35份，其中海藻酸钠水溶液的体积浓度为0.5g/100mL，所述固化剂为3-异氰酸酯基亚甲基-3，5，5-三甲基环己基异氰酸酯，所述颜填料由有机改性蒙脱土、钛白粉和煅烧高岭土按质量比为1:2:5混合而成，所述助剂由3份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、5份十二醇酯成膜助剂、0.1份有机硅消泡流平剂、1份由5-氯-2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂混合而成的防霉防藻剂和0.01份乙醇胺类中和剂，所述溶剂由聚乙二醇400和水按体积比为1:10混合而成。
本实施例中改性聚偏二氟乙烯乳液原料组分按原料重量份计包括聚偏二氟乙烯树脂粉末15份、改性剂5份、引发剂1份、溶剂60份，其中改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成，引发剂为BPO。
改性聚偏二氟乙烯乳液的制备方法：
1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:3混合而成的溶剂中，加热至50℃，搅拌30min充分反应，加入纯化的改性剂，混合均匀；
2)在氮气气氛中加入引发剂，在70℃的氮气气氛中下继续搅拌反应6h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；
5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:3:3的混合溶液中，搅拌分散均匀，得到实施例1改性聚偏二氟乙烯乳液。
水性聚偏二氟乙烯涂料的制备方法：
1)将分散剂、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)将白色漆浆与改性聚偏二氟乙烯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水性聚偏二氟乙烯涂料成品。
实施例2
本实施例中水性聚偏二氟乙烯涂料原料组分按原料重量份计包括改性聚偏二氟乙烯乳液60份、海藻酸钠水溶液5份、固化剂7份、颜填料15份、助剂15份、溶剂5份，其中海藻酸钠水溶液的体积浓度为1g/100mL，所述固化剂为缩二脲多异氰酸酯，所述颜填料由有机改性蒙脱土、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0.5份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、5份有机硅消泡流平剂、0.05份由2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂混合而成的防霉防藻剂和5份乙醇胺类中和剂，所述溶剂由聚乙二醇400和水按体积比为1:5混合而成。
本实施例中改性聚偏二氟乙烯乳液原料组分按原料重量份计包括聚偏二氟乙烯树脂粉末10份、改性剂10份、引发剂0.5份、溶剂75份，其中改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成，引发剂为AIBN。
改性聚偏二氟乙烯乳液的制备方法：
1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:2混合而成的溶剂中，加热至80℃，搅拌15min充分反应，加入纯化的改性剂，混合均匀；
2)在氮气气氛中加入引发剂，在80℃的氮气气氛中下继续搅拌反应6h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；
5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:2:9的混合溶液中，搅拌分散均匀，得到实施例2改性聚偏二氟乙烯乳液。
水性聚偏二氟乙烯涂料的制备方法：
1)将分散剂、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)将白色漆浆与改性聚偏二氟乙烯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1500rpm的速度搅拌15min，再加入防霉防藻剂，经研磨，得实施例2水性聚偏二氟乙烯涂料成品。
实施例3
本实施例中水性聚偏二氟乙烯涂料原料组分按原料重量份计包括改性聚偏二氟乙烯乳液50份、海藻酸钠水溶液8份、固化剂5份、颜填料23份、助剂10份、溶剂20份，其中海藻酸钠水溶液的体积浓度为0.8g/100mL，所述固化剂为3-异氰酸酯基亚甲基-3，5，5-三甲基环己基异氰酸酯，所述颜填料由有机改性蒙脱土、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1.5份0.2％体积浓度的聚丙烯酰胺水溶液分散剂、1份非离子缔合型聚氨酯增稠剂、3份十二醇酯成膜助剂、3份有机硅消泡流平剂、0.5份由5-氯-2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂混合而成的防霉防藻剂和2份乙醇胺类中和剂，所述溶剂由聚乙二醇400和水按体积比为1:8混合而成。
本实施例中改性聚偏二氟乙烯乳液原料组分按原料重量份计包括聚偏二氟乙烯树脂粉末12份、改性剂8份、引发剂0.8份、溶剂70份，其中改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成，引发剂为AIBN。
改性聚偏二氟乙烯乳液的制备方法：
1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:2.5混合而成的溶剂中，加热至65℃，搅拌20min充分反应，加入纯化的改性剂，混合均匀；
2)在氮气气氛中加入引发剂，在75℃的氮气气氛中下继续搅拌反应7h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；
5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:3:5的混合溶液中，搅拌分散均匀，得到实施例3改性聚偏二氟乙烯乳液。
水性聚偏二氟乙烯涂料的制备方法：
1)将分散剂、成膜助剂、消泡流平剂和溶剂混合，以1500rpm的速度搅拌12min，再以2500rpm的速度搅拌25min，得白色漆浆；
2)将白色漆浆与改性聚偏二氟乙烯乳液和海藻酸钠水溶液混合，于1500rpm速度下搅 拌25min，加入pH调节剂，调节pH＝8，加入增稠剂，以1800rpm的速度搅拌12min，再加入防霉防藻剂，经研磨，得实施例3水性聚偏二氟乙烯涂料成品。
实施例4
本实施例中水性聚偏二氟乙烯涂料原料组分按原料重量份计包括改性聚偏二氟乙烯乳液55份、海藻酸钠水溶液6份、固化剂4份、颜填料25份、助剂12份、溶剂30份，其中海藻酸钠水溶液的体积浓度为1g/100mL，所述固化剂为缩二脲多异氰酸酯，所述颜填料由有机改性蒙脱土、钛白粉和煅烧高岭土按质量比为1:4:8混合而成，所述助剂由1份0.2％体积浓度的聚丙烯酰胺水溶液分散剂、1份非离子缔合型聚氨酯增稠剂、4份十二醇酯成膜助剂、1份有机硅消泡流平剂、1份由2-甲基-4异噻唑啉-3-酮与释放甲醛型防腐剂混合而成的防霉防藻剂和1份乙醇胺类中和剂，所述溶剂由聚乙二醇400和水按体积比为1:8混合而成。
本实施例中改性聚偏二氟乙烯乳液原料组分按原料重量份计包括聚偏二氟乙烯树脂粉末10份、改性剂8份、引发剂1份、溶剂60份，其中改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成，引发剂为AIBN。
改性聚偏二氟乙烯乳液的制备方法：
1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:3混合而成的溶剂中，加热至80℃，搅拌15min充分反应，加入纯化的改性剂，混合均匀；
2)在氮气气氛中加入引发剂，在80℃的氮气气氛中下继续搅拌反应8h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；
3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；
5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:3:5的混合溶液中，搅拌分散均匀，得到实施例4改性聚偏二氟乙烯乳液。
水性聚偏二氟乙烯涂料的制备方法：
1)将分散剂、成膜助剂、消泡流平剂和溶剂混合，以1500rpm的速度搅拌10min，再以3000rpm的速度搅拌20min，得白色漆浆；
2)将白色漆浆与改性聚偏二氟乙烯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15min，再加入防霉防藻剂，经研磨，得实施例4水性聚偏二氟乙烯涂料成品。
实施例5：性能检测数据
将实施例1～4制备得的水性聚偏二氟乙烯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
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)
- 一种水性聚偏二氟乙烯涂料，其特征在于按原料重量份计包括如下组分：改性聚偏二氟乙烯乳液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、溶剂5～35份，所述改性聚偏二氟乙烯乳液经甲基丙烯酸2-羟乙酯和氧乙烯甲基丙烯酸酯接枝改性。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述改性聚偏二氟乙烯乳液按原料重量份计包括聚偏二氟乙烯树脂粉末10～15份、改性剂5～10份、引发剂0.5～1份、溶剂60～75份，其中所述改性剂由聚甲基丙烯酸2-羟乙酯和聚氧乙烯甲基丙烯酸酯组成。
- 根据权利要求2所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述引发剂为BPO或AIBN。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述改性聚偏二氟乙烯乳液的制备方法包括如下步骤：1)将聚偏二氟乙烯树脂粉末分散到由磷酸三乙酯和酰胺按体积比为1:2～3混合而成的溶剂中，加热至50～80℃，搅拌15～30min充分反应，加入纯化的改性剂，混合均匀；2)在氮气气氛中加入引发剂，在70～80℃的氮气气氛中下继续搅拌反应6～8h，撤去氮气气氛，加入去离子水，得到沉淀粗产物；3)沉淀粗产物真空过滤成滤饼，洗涤烘干，得到改性聚偏二氟乙烯树脂；5)将步骤4)所得的改性聚偏二氟乙烯树脂加入到由磷酸三乙酯、3,5,5-三甲基-2-环己烯酮与水按体积比为1:2～3:3～9的混合溶液中，搅拌分散均匀，得到改性聚偏二氟乙烯乳液。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述海藻酸钠水溶液的体积浓度为0.5～1g/100mL。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述固化剂为氰酸酯类化合物。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，其特征在于：所述颜填料由有机改性蒙脱土、钛白粉和煅烧高岭土按质量比为1:2～4:5～10混合而成。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，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。
- 根据权利要求1所述的一种水性聚偏二氟乙烯涂料，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。
- 一种如权利要求1～9任一项所述的水性聚偏二氟乙烯涂料的制备方法，其特征在于包括如下工艺步骤：1)将颜填料、固化剂、润湿剂、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)将白色漆浆与改性聚偏二氟乙烯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，得水性聚偏二氟乙烯涂料成品。
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| EP0193963A2 (en) * | 1985-03-06 | 1986-09-10 | Daikin Industries, Limited | Aqueous dispersion comprising fluorine-containing copolymer and article coated therewith |
| CN103571284A (zh) * | 2013-09-29 | 2014-02-12 | 青岛市高科专利技术转移平台有限公司 | 一种玻璃墙用防尘涂料 |
| CN108753054A (zh) * | 2018-06-29 | 2018-11-06 | 佛山市高明区爪和新材料科技有限公司 | 一种水性防腐漆 |
| 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 |
| CN110511642A (zh) * | 2019-08-26 | 2019-11-29 | 佛山科学技术学院 | 一种水性聚偏二氟乙烯涂料及其制备方法 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101876179B1 (ko) * | 2009-06-10 | 2018-07-10 | 알케마 인코포레이티드 | 내후성 폴리비닐리덴 플루오라이드로 피복된 기재 |
| CN108976937A (zh) * | 2018-07-16 | 2018-12-11 | 安徽博泰氟材料科技有限公司 | 一种高阻燃性氟碳漆及其制备方法 |
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Patent Citations (7)
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|---|---|---|---|---|
| FR1196881A (fr) * | 1956-10-16 | 1959-11-26 | Minnesota Mining & Mfg | Latex d'oléfine perfluorohalogénée |
| EP0193963A2 (en) * | 1985-03-06 | 1986-09-10 | Daikin Industries, Limited | Aqueous dispersion comprising fluorine-containing copolymer and article coated therewith |
| CN103571284A (zh) * | 2013-09-29 | 2014-02-12 | 青岛市高科专利技术转移平台有限公司 | 一种玻璃墙用防尘涂料 |
| CN108753054A (zh) * | 2018-06-29 | 2018-11-06 | 佛山市高明区爪和新材料科技有限公司 | 一种水性防腐漆 |
| 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 |
| CN110511642A (zh) * | 2019-08-26 | 2019-11-29 | 佛山科学技术学院 | 一种水性聚偏二氟乙烯涂料及其制备方法 |
| 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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