WO2020000918A1 - 阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法 - Google Patents

阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法 Download PDF

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WO2020000918A1
WO2020000918A1 PCT/CN2018/120888 CN2018120888W WO2020000918A1 WO 2020000918 A1 WO2020000918 A1 WO 2020000918A1 CN 2018120888 W CN2018120888 W CN 2018120888W WO 2020000918 A1 WO2020000918 A1 WO 2020000918A1
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parts
weight
water
flame
added
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段小宁
何宏昌
段立明
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周连惠
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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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • 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

Definitions

  • the invention relates to a method for preparing an aqueous core-shell type acrylic resin, in particular to a method for preparing a flame-retardant and waterproof water-based core-shell acrylic resin coating and paint.
  • Paint traditional Chinese name for paint.
  • the so-called coating is a continuous film that is coated on the surface of the object to be protected or decorated and can form a strong adhesion with the object to be coated. It is usually based on resin, oil, or emulsion, with or without pigments, fillers, and additives. Corresponding auxiliaries, viscous liquids prepared with organic solvents or water.
  • the service life of the coating is determined by different products.
  • the liquid marble texture product uses modified silicone resin emulsion as the base material and uses special coating technology to coat various colors of paint into colloidal water-based color particles, which are uniform and stable. Suspended in a specific aqueous dispersion, the hue of various colored particles remains unchanged, and the colored pigment does not precipitate in water. Then the service life of this exterior coating is about 15 years.
  • Water-based coatings and powder coatings have become a climate, especially architectural coatings based on water-based paints, which have accounted for about 38% of China's total coatings. Because the chemical characteristics of water-based paints and oil-based paints are essentially different, and the properties of water-based paints and oil-based paints are also very different, it is unscientific to set water-based paints as a large branch of the paint industry. .
  • the form of the product it can be divided into: liquid paint, powder paint, high solid paint.
  • anti-corrosion coating anti-rust coating
  • insulation coating high temperature resistant coating
  • aging resistant coating acid and alkali resistant coating
  • chemical medium resistant coating (4) According to its performance, it can be divided into: anti-corrosion coating, anti-rust coating, insulation coating, high temperature resistant coating, aging resistant coating, acid and alkali resistant coating, and chemical medium resistant coating.
  • (6) According to its construction process, it can be divided into: closed paint, putty, primer, two primers, topcoat, and finish paint.
  • (7) According to the construction method, it can be divided into brush coating, spray coating, roller coating, dip coating and electrophoretic coating.
  • (8) According to function, it can be divided into non-stick coating, Teflon coating, decorative coating, anticorrosive coating, conductive coating, rust-proof coating, high-temperature-resistant coating, temperature-indicating coating, heat-insulating coating, fire-proof coating, and waterproof coating.
  • Household paint can be divided into interior wall paint, exterior wall paint, wood paint, metal paint and floor paint.
  • Inorganic coatings refer to coatings produced using inorganic polymer materials as the base material, including water-soluble silicate-based, silica-sol-based, silicone, and inorganic polymer-based.
  • Organic-inorganic composite coatings have two composite forms. One is the use of organic and inorganic materials as the base material in the production of the coating to form a composite coating; the other is the combination of organic and inorganic coatings during decorative construction.
  • Classification according to decorative effects can be divided into: 1. flat and smooth surface coating (commonly known as flat coating), which is the most common method of construction; 2. sand wall-like coating with sand-like decorative effect on the surface, such as real stone paint; 3. Multi-layer coating for forming three-dimensional decorative effect of concave and convex pattern, such as relief.
  • flat coating commonly known as flat coating
  • sand wall-like coating with sand-like decorative effect on the surface such as real stone paint
  • Multi-layer coating for forming three-dimensional decorative effect of concave and convex pattern, such as relief.
  • Classified according to the use site on the building divided into interior wall paint, exterior wall paint, floor paint, door and window paint and ceiling paint.
  • Classification by use function It can be divided into ordinary coatings and special functional architectural coatings (such as fire-resistant coatings, waterproof coatings, mildew-proof coatings, road marking coatings, etc.).
  • color effect classification such as metal paint, natural paint (also known as: solid paint), transparent varnish and so on.
  • the present invention relates to the field of production and preparation of polymer products, in particular to an acrylic resin flame retardant coating, 12-18 parts of amino resin, 3-6 parts of ethyl acrylate, 3-5 parts of butyl acrylate, and 2-10 parts of melamine 1-2 parts defoamer, 2-6 parts pigment and filler, 2-3 parts acrylic acid, 60-70 parts by weight of carboxyl-containing anionic water-based resin, 5-10 parts by weight water-resistant pigment, 7-8 parts by weight Auxiliaries, 1 to 2 parts by weight of interfacial adhesion promoter, 4 to 8 parts of carbon forming agent, 10 to 20 parts by weight of deionized water; interfacial adhesion promoter consists of metal organics, polyisocyanates, and oligomers containing hydroxyl groups ⁇ ⁇ From the reaction.
  • the acrylic resin coating of the present invention has excellent interfacial adhesion between the substrate and the substrate, and has a good flame retardant effect.
  • Flame retardant, antibacterial and waterproof graphene modified acrylic resin coating preparation method 201610331925.3 discloses a method for preparing flame retardant, antibacterial and waterproof graphene modified acrylic resin coating. After peeling the walnut green peel, it is washed with water and placed in an oven. Dry to constant weight at 40 ⁇ 70 °C, crush and pass through 80 ⁇ 100 mesh sieve to obtain walnut green peel powder, weigh walnut green peel powder and water, add allyltrimethylammonium chloride, 4-methoxy Methyl acetoacetate is cooked under reflux at 80-100 ° C, the boiling liquid is filtered, and the solution is concentrated under reduced pressure at 60-70 ° C.
  • a walnut green peel extract concentrate is obtained and used in an acrylate resin, and the obtained acrylate resin has antibacterial, flame retardancy and good water resistance.
  • the invention relates to a method for preparing flame-retardant and water-resistant core-shell acrylic resin coatings and paints.
  • the main idea of the invention is to modify the intumescent flame retardant and water-repellent agent with vinyl monomers. Branched into acrylic resin, specifically using vinylphosphine as a bridge, with the assistance of 2-aminoisobutyric acid, the intumescent flame retardant was reacted into the acrylic resin, while acrylic acid and hydroxyethyl acrylate were used in the aminotrimethyl methacrylate.
  • the water-repellent agent was grafted into the acrylic resin under the action of the phosphonic acid and tetramethylethylenediamine, and the flame-retardant and water-repellent water-based core-shell type acrylic resin coating and paint were obtained under the action of the self-made crosslinking agent.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 3 to 8 parts by weight of butyl acrylate, 2 to 6 parts by weight of methyl methacrylate, and 3 to 3.5 parts by weight of ethyl acrylate;
  • step (1) (4) adding monomer B, 0.3 to 0.6 parts by weight of initiator A and 4.4 parts by weight of flame retardant obtained in step (1) to the core layer emulsion obtained in step (3) simultaneously, and the dropping time lasts for 1 to 4 hours, After the dropwise addition, the temperature was kept at 75-85 ° C, and the reaction was stirred for 2h, then 0.5 to 1.0 parts by weight of the cross-linking agent was added, the reaction time was maintained at 75-85 ° C, and the reaction time was 1 to 2h.
  • the reaction time is 30 minutes, and the pH value is adjusted to 7 to 8 by adding ammonia water to obtain the flame-retardant and waterproof water-based core-shell acrylic resin coating and paint;
  • the monomer B is made of: acrylic acid 4 to 8 parts by weight of butyl ester, 3 to 6 parts by weight of methyl methacrylate, and 3 to 5 parts by weight of ethyl acrylate are mixed.
  • the catalyst A is any of 2,4-dichloronitrobenzene, p-nitroaniline, hydroxylamine sulfate, and hydroxylamine chloride.
  • Emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinyl phosphine is any one of vinyl ethyl phosphonic acid and vinyl phosphonic acid; initiation Agent A is any one of ammonium persulfate and potassium persulfate; the preparation method of the cross-linking agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxymalonic acid into a three-necked flask At 90 ° C, 6.2g of pentaerythritol and 4.1g of trimethylolpropane were added, and the reaction was held for 2 to 4 hours. Then, 1.1g of 7-hydroxycoumarin-3-carboxylic acid was added, and the reaction was performed at 110 ° C for 3-4 hours.
  • Crosslinking agent is a mixture of sodium dodecylbenzenesulfonate and
  • the flame retardant is an intumescent flame retardant, which has a good residual carbon rate and expandability to promote the surface of the acrylic resin to have a more dense carbon layer.
  • the expandability has a thermally non-conductive body, which reduces the external heat. The tendency to continue to burn.
  • step (3) and step (4) of the acrylic resin preparation are all dissolved with 5 g of water.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 3 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
  • step (3) To the core layer emulsion obtained in step (3), simultaneously dropwise add B monomer, 0.3 parts by weight of initiator A (dissolved with 5 parts by weight of water) and 4.4 parts by weight of the flame retardant obtained in step (1). The time lasted for 1h. After the dropwise addition, the reaction was stirred at 75 ° C for 2h, then 0.5 parts by weight of cross-linking agent was added, the reaction time was maintained at 75 ° C for 1h, the temperature was lowered to 50 ° C, 0.3 parts by weight of emulsifier was added, and the waterproof obtained in step (2) was added. 0.7 parts of the agent, the reaction time is 30 minutes, and the pH value is adjusted to 7 to 8 by adding ammonia water to obtain the flame-retardant and waterproof water-based core-shell acrylic resin coatings and paints;
  • the B monomer is formed by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate.
  • Its catalyst A is 2,4-dichloronitrobenzene.
  • the emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinyl phosphine is diethyl vinylphosphonate; initiator A is ammonium persulfate; said
  • the method for preparing the crosslinking agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxymalonic acid into a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 ° C. After incubation for 2 h, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the reaction was carried out at 110 ° C. for 3 h to obtain the crosslinking agent.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate, and 3.5 parts by weight of ethyl acrylate;
  • the B monomer is prepared by mixing 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
  • Its catalyst A is p-nitroaniline.
  • Emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinylphosphine is vinylphosphonic acid; initiator A is potassium persulfate; said cross-linking
  • the preparation method of the agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxyglycidylcarboxylic acid to a three-necked flask, adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 ° C, and holding the reaction for 4 hours Then, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added and reacted at 110 ° C. for 4 hours to obtain the crosslinking agent.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 5.5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 3.3 parts by weight of ethyl acrylate;
  • the B monomer is a mixture of 6 parts by weight of butyl acrylate, 4.5 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
  • Its catalyst A is hydroxylamine sulfate.
  • the emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinyl phosphine is diethyl vinylphosphonate; initiator A is ammonium persulfate; said
  • the method for preparing the crosslinking agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxymalonic acid into a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 ° C. After incubation for 3 hours, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added and reacted at 110 ° C for 3.5 hours to obtain the crosslinking agent.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 3 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate, and 3.5 parts by weight of ethyl acrylate;
  • the B monomer is prepared by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
  • Its catalyst A is hydroxylamine chloride.
  • the emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinyl phosphine is diethyl vinylphosphonate; initiator A is ammonium persulfate; said The method for preparing the crosslinking agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxymalonic acid into a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 ° C. After incubation for 2 hours, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added and reacted at 110 ° C for 4 hours to obtain the crosslinking agent.
  • a method for preparing a flame-retardant and water-resistant core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 8 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
  • the B monomer is prepared by mixing 5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
  • Its catalyst A is p-nitroaniline.
  • the emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4: 1; vinylphosphine is diethyl vinylphosphonate; initiator A is potassium persulfate; said The method for preparing the crosslinking agent is: adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxymalonic acid into a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 ° C. After incubation for 3 hours, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added and reacted at 110 ° C for 3 hours to obtain the crosslinking agent.
  • the flame retardancy is measured by the oxygen index and flame burning time. Among them, the flame retardancy and light resistance are measured by the performance and expansion of the film formed by the acrylic resin coating.
  • the muffle furnace is heated to 500 ° C.
  • a crucible with 1 g (with an error not exceeding 0.1 g) was placed in a muffle furnace and heated for 10 minutes, and the expansion rate and residual carbon ratio were measured (only the flame retardant was measured).

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Abstract

一种阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，向反应容器中加入以下重量配比的原料：水55～75份、乳化剂0.2～2.2份、丙烯酸0.6～3.0份，升温至50℃，搅拌30min，加入A单体，乳化时间为30～60min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.2～0.6重量份，滴加时间持续1～2h，滴加完后反应2～5h，得核层乳液；向所得核层乳液中同时滴加B单体、0.3～0.6重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续1～4h，滴加完后保温75～85℃搅拌反应2h，再加入交联剂0.5～1.0重量份，保温75～85℃反应时间1～2h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆，该材料可用于内外墙涂料、金属涂饰和防腐、做木材的油漆及其作为皮革涂饰剂。

Description

阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法 技术领域
本发明涉及到水性核壳型丙烯酸酯类树脂的制备方法，尤其是阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法。
背景技术
涂料，在中国传统名称为油漆。所谓涂料是涂覆在被保护或被装饰的物体表面，并能与被涂物形成牢固附着的连续薄膜，通常是以树脂、或油、或乳液为主，添加或不添加颜料、填料，添加相应助剂，用有机溶剂或水配制而成的粘稠液体。
新中国成立60年来，伴随着国民经济各行业的发展，作为其配套的涂料工业从一个极不引人注目的小行业逐步发展成为国民经济各领域必不可少的重要行业。经过几代人的顽强拼搏、开拓进取，我国已成为世界第二大涂料生产国和消费国，进入到世界涂料行业发展的主流。
涂料的使用寿命根据不同的产品而定的，液态理石质感产品采用改性有机硅树脂乳液为基料，运用特殊包覆技术，将各色色漆包覆成胶状水性彩色颗粒，均匀稳定地悬浮在特定的水性分散体中，各种着色粒子色相保持不变，着色颜料不会在水中析出。那么这种外墙涂料的使用寿命大概为15年。
水性涂料与粉末涂料已成气候，尤其是以水性漆为主的建筑涂料已在我国涂料总量中占到约38％。由于水性漆与油性漆其化学特性有本质上的区别，水性漆与油性漆产品性质也有很大的差异，那么再把水性漆定为油漆行业中的一大分支的陈旧理解，是不科学的。
涂料的分类方法很多，通常有以下几种分类方法：
(1))按产品的形态来分，可分为：液态涂料、粉末型涂料、高固体分涂料。
(2)按涂料使用分散介质：溶剂型涂料；水性涂料(乳液型涂料、水溶性涂料)。
(3))按用途可分为建筑涂料、罐头涂料、汽车涂料、飞机涂料、家电涂料、木器涂料、桥梁涂料、塑料涂料、纸张涂料、船舶涂料、风力发电涂料、核电涂料、管道涂料、钢结构涂料、橡胶涂料、航空涂料等。
(4)按其性能来分，可分为：防腐蚀涂料、防锈涂料、绝缘涂料、耐高温涂料、耐老化涂料、耐酸碱涂料、耐化学介质涂料。
(5))按是否有颜色，可分为：清漆、色漆。
(6)按其施工工序来分，可分为：封闭漆、腻子、底漆、二道底漆、面漆、罩光漆。
(7)按施工方法可分为刷涂涂料、喷涂涂料、辊涂涂料、浸涂涂料、电泳涂料等。
(8)按功能可分为不粘涂料、铁氟龙涂料、装饰涂料、防腐涂料、导电涂料、防锈涂料、耐高温涂料、示温涂料、隔热涂料、防火涂料、防水涂料等。
(9)家用油漆可分为内墙涂料、外墙涂料、木器漆、金属用漆、地坪漆。
(10)按漆膜性能分(防腐漆、绝缘漆、导电漆、耐热漆……)(11)按成膜物质分(天然树脂类漆、酚醛类漆、醇酸类漆、氨基类漆、硝基类漆、环氧类漆、氯化橡胶类漆、丙烯酸类漆、聚氨酯类漆、有机硅树脂类漆、氟碳树脂类漆、聚硅氧烷类漆、乙烯树脂类漆……)(12)按基料的种类分类：可分为有机涂料、无机涂料、有机—无机复合涂料。有机涂料由于其使用的溶剂不同，又分为有机溶剂型涂料和有机水性(包括水乳型和水溶型)涂料两类。生活中常见的涂料一般都是有机涂料。无机涂料指的是用无机高分子材料为基料所生产的涂料，包括水溶性硅酸盐系、硅溶胶系、有机硅及无机聚合物系。有机—无机复合涂料有两种复合形式，一种是涂料在生产时采用有机材料和无机材料共同作为基料，形成复合涂料；另一种是有机涂料和无机涂料在装饰施工时相互结合。
按装饰效果分类：可分为：1.表面平整光滑的平面涂料(俗称平涂)，这是最为常见的一种施工方式；2.表面呈砂粒状装饰效果的砂壁状涂料，如真石漆；3.形成凹凸花纹立体装饰效果的复层涂料，如浮雕。
按在建筑物上的使用部位分类：分为内墙涂料、外墙涂料、地面涂料、门窗涂料和顶棚涂料。
按使用功能分类：可分为普通涂料和特种功能性建筑涂料(如防火涂料、防水涂料、防霉涂料、道路标线涂料等)。
按照使用颜色效果分类：如金属漆，本色漆(或者叫作：实色漆)，透明清漆等。
201610645798.4本发明涉及高分子产品的生产制备领域，尤其涉及一种丙烯酸树脂阻燃涂料，12-18份氨基树脂、3-6份丙烯酸乙酯、3-5份丙烯酸丁酯、2-10份三聚氰胺、1-2份消泡剂、2-6份颜填料、2-3份丙烯酸、60～70重量份的含羧基的阴离子水性树脂、5～10重量份的耐水颜料、7～8重量份的助剂、1～2重量份的界面附着力增进剂、4-8份成炭剂、10～20重量份的去离子水；界面附着力增进剂由金属有机物、多异氰酸酯和含有羟基的低聚物反应而成。本发明的丙烯酸树脂涂料与基材之间具有优异的界面附着力并且具有很好的阻燃效果。
阻燃、抗菌、防水石墨烯改性丙烯酸酯树脂涂料制备方法201610331925.3公开了阻燃、抗菌、防水石墨烯改性丙烯酸酯类树脂涂料制备方法，将核桃青皮剥离后用水洗净，置于烘箱内40～70℃温度下烘干至恒重，粉碎并过80～100目筛，得核桃青皮粉末，称取核桃青皮粉末及水，加入烯丙基三甲基氯化铵、4-甲氧基乙酰乙酸甲酯于80～100℃温度下回流煎煮，过滤煎煮液，60～70℃温度下减压浓缩，待浓缩液成水含量在15％～20％的浓膏状至恒重即可，得到核桃青 皮提取物浓缩液，并用于丙烯酸酯类树脂中，所得丙烯酸酯类树脂具有抗菌、阻燃和防水性好。
发明内容
本发明涉及到阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，是构思的主要思路是在将膨胀性阻燃剂和防水剂用乙烯基单体进行改性，可以接枝到丙烯酸树脂中，具体而言是用乙烯基膦作为桥梁，在2-氨基异丁酸的协助下将膨胀性阻燃剂反应到丙烯酸树脂中，同时用丙烯酸、丙烯酸羟乙酯在氨基三甲叉膦酸和四甲基乙二胺的作用下将防水剂接枝到丙烯酸树脂中，并用自制的交联剂的作用下，得到阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆。
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，90-120℃反应3～5h，降温到70～80℃，反应2～5h，再升温到90～100℃，加入1～2mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间2～6h，得到该阻燃剂；
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰 胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，即得该防水剂；
(3)向反应容器中加入以下重量配比的原料：水55～75份、乳化剂0.2～2.2份、丙烯酸0.6～3.0份，升温至50℃，搅拌30min，加入A单体，乳化时间为30～60min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.2～0.6重量份，滴加时间持续1～2h，滴加完后反应2～5h，得核层乳液；
所述A单体是由：丙烯酸丁酯3～8重量份、甲基丙烯酸甲酯2～6重量份、丙烯酸乙酯3～3.5重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.3～0.6重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续1～4h，滴加完后保温75～85℃搅拌反应2h，再加入交联剂0.5～1.0重量份，保温75～85℃反应时间1～2h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；所述B单体是由：丙烯酸丁酯4～8重量份、甲基丙烯酸甲酯3～6重量份、丙烯酸乙酯3～5重量份混合而成。
其催化剂A为2,4-二氯硝基苯、对硝基苯胺、硫酸羟胺、氯化羟胺的任意一种。
乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸二乙酯、乙烯基膦酸的任意一种；引发剂A为过硫酸铵、过硫酸钾的任意一种；所述的交联剂 的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应2～4h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应3-4h，得该交联剂。
本发明的优势在于：
(1)选择2,4-二氯硝基苯、对硝基苯胺、硫酸羟胺、氯化羟胺作为膨胀性阻燃剂的催化剂；具有无毒、效率高的优势；
(2)阻燃剂为膨胀型阻燃剂，具有良好的剩炭率和膨胀性，来促使丙烯酸树脂表面具有较多的致密炭层，同时膨胀性具有热的不导热体，降低了外部热量继续燃烧的倾向。
(3)将膨胀性阻燃剂和防水剂用乙烯基单体进行改性，可以接枝到丙烯酸树脂中，具体而言是用乙烯基膦作为桥梁，在2-氨基异丁酸的协助下将膨胀性阻燃剂反应到丙烯酸树脂中，同时用丙烯酸、丙烯酸羟乙酯在氨基三甲叉膦酸和四甲基乙二胺的作用下将防水剂接枝到丙烯酸树脂中，并用自制的交联剂的作用下，得到阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆。
(4)在丙烯酸树脂制备的步骤(3)和步骤(4)未特别说明的引发剂，均用5g水溶解。
具体实施方式
实例1
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，90℃反应3h，降温到70℃，反应2h，再升温到90℃，加入1mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间2h，得到该阻燃剂；
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，即得该防水剂；
(3)向反应容器中加入以下重量配比的原料：水55份、乳化剂0.2份、丙烯酸0.6份，升温至50℃，搅拌30min，加入A单体，乳化时间为30min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.2重量份(用5重量份水溶解)，滴加时间1h，滴加完后反应2h，得核层乳液；
所述A单体是由：丙烯酸丁酯3重量份、甲基丙烯酸甲酯2重量份、丙烯酸乙酯3重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.3重量份的引发剂A(用5重量份水溶解)和步骤(1)所得阻燃剂4.4重量份，滴加时间持续1h，滴加完后，保温75℃搅拌反应2h，再加入交联剂0.5重量份，保温75℃反应时间1h，降温到50℃，加入乳化剂0.3 重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
所述B单体是由：丙烯酸丁酯4重量份、甲基丙烯酸甲酯3重量份、丙烯酸乙酯3重量份混合而成。
其催化剂A为2,4-二氯硝基苯。
乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸二乙酯；引发剂A为过硫酸铵；所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应2h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应3h，得该交联剂。
实例2
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，120℃反应5h，降温到80℃，反应5h，再升温到100℃，加入2mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间6h，得到该阻燃剂；
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，即得该防水剂；
(3)向反应容器中加入以下重量配比的原料：水75份、乳化剂2.2份、丙烯酸3.0份，升温至50℃，搅拌30min，加入A单体，乳化时间为60min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.6重量份，滴加时间持续2h，滴加完后反应5h，得核层乳液；
所述A单体是由：丙烯酸丁酯8重量份、甲基丙烯酸甲酯6重量份、丙烯酸乙酯3.5重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.6重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续4h，滴加完后保温85℃搅拌反应2h，再加入交联剂1.0重量份，保温85℃反应时间2h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
所述B单体是由：丙烯酸丁酯8重量份、甲基丙烯酸甲酯6重量份、丙烯酸乙酯5重量份混合而成。
其催化剂A为对硝基苯胺。
乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸；引发剂A为过硫酸钾；所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应4h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应4h，得该交联剂。
实例3
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，105℃反应4h，降温到75℃，反应3.5h，再升温到95℃，加入1.5mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间4h，得到该阻燃剂。
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，即得该防水剂；
(3)向反应容器中加入以下重量配比的原料：水65份、乳化剂1.2份、丙烯酸1.8份，升温至50℃，搅拌30min，加入A单体，乳化时间为45min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.4重量份，滴加时间持续1.5h，滴加完后反应2.5h，得核层乳液；
所述A单体是由：丙烯酸丁酯5.5重量份、甲基丙烯酸甲酯4重量份、丙烯酸乙酯3.3重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.45重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续2.5h，滴加完后保温80℃搅拌反应2h，再加入交联剂0.75重量份，保温80℃反应时间1.5h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
所述B单体是由：丙烯酸丁酯6重量份、甲基丙烯酸甲酯4.5重量份、丙烯酸乙酯4重量份混合而成。
其催化剂A为硫酸羟胺。
乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸二乙酯；引发剂A为过硫酸铵；所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应3h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应3.5h，得该交联剂。
实例4
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，90℃反应5h，降温到80℃，反应5h，再升温到100℃，加入2mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间3h，得到该阻燃剂。
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，得该防水剂；
(3)向反应容器中加入以下重量配比的原料：水60份、乳化剂1份、丙烯酸2份，升温至50℃，搅拌30min，加入A单体，乳化时间为45min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.2重量份，滴加时间持续1h，滴加完后反应2h，得核层乳液；
所述A单体是由：丙烯酸丁酯3重量份、甲基丙烯酸甲酯6重量份、丙烯酸乙酯3.5重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.6重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续4h，滴加完后保温85℃搅拌反应2h，再加入交联剂1.0重量份，保温85℃反应时间2h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
所述B单体是由：丙烯酸丁酯4重量份、甲基丙烯酸甲酯3重量份、丙烯酸乙酯5重量份混合而成。
其催化剂A为氯化羟胺。乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸二乙酯；引发剂A为过硫酸铵；所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应2h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应4h，得该交联剂。
实例5
阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
(1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，120℃反应3h，降温到70℃，反应2h，再升温到90℃，加 入1mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间2h，得到该阻燃剂。
(2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，得该防水剂。
(3)向反应容器中加入以下重量配比的原料：水55份、乳化剂2.2份、丙烯酸3.0份，升温至50℃，搅拌30min，加入A单体，乳化时间为60min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.6重量份，滴加时间持续2h，滴加完后反应5h，得核层乳液；
所述A单体是由：丙烯酸丁酯8重量份、甲基丙烯酸甲酯2重量份、丙烯酸乙酯3重量份混合而成；
(4)向步骤(3)所得核层乳液中同时滴加B单体、0.3重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续1h，滴加完后保温75℃搅拌反应2h，再加入交联剂0.5重量份，保温75℃反应时间1h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
所述B单体是由：丙烯酸丁酯5重量份、甲基丙烯酸甲酯4重量份、丙烯酸乙酯4重量份混合而成。
其催化剂A为对硝基苯胺。乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物；乙烯基膦为乙烯基膦酸二乙酯；引发剂A为过硫酸钾；所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应3h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应3h，得该交联剂。
阻燃性通过氧指数、有焰燃烧时间来衡量，其中阻燃性和耐光性均为测定其丙烯酸酯类树脂涂料所成膜的性能和膨胀性是将马弗炉加热到500℃，将装有1g(误差不超过0.1g)的坩埚，置于马弗炉中加热10min，测量膨胀率和剩炭率(只是测定阻燃剂)。
表1 测试性能
Figure PCTCN2018120888-appb-000001
从表1可以看出，该聚氨酯涂料与胶黏剂在氧指数、有焰燃烧时间和防水性方面均优于背景技术中所提及的发明专利的性能，由于篇幅所限，申请人对201610331925.3的实例1和201610645798.4的实例 2均作了氧指数和有焰燃烧时间的测试，发现其氧指数分别为26.2和22.9，其有焰燃烧时间分别为19.8和16.8。
表2 测试性能(未加催化剂A)
Figure PCTCN2018120888-appb-000002
从表2可以看出，未加催化剂A的氧指数、有焰燃烧时间、剩炭率和膨胀率均下降。
表3 测试性能(加催化剂A，未加2-氨基异丁酸)
Figure PCTCN2018120888-appb-000003
从表3可以看出，2-氨基异丁酸提高了阻燃性能的各个指标。
表4 测试性能(未加交联剂)
Figure PCTCN2018120888-appb-000004
从表4可以看出，未加交联剂所得数据大部分漏水。
表5测试性能(未加防水剂)
Figure PCTCN2018120888-appb-000005
从表5可以看出，未加防水剂，所得材料漏水。
表6测试性能(加防水剂，未加氨基三甲叉膦酸或四甲基乙二胺)
Figure PCTCN2018120888-appb-000006
从表6可以看出，未加氨基三甲叉膦酸或四甲基乙二胺，所得材料部分漏水。

Claims (6)

  1. 阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，其制备方法为：
    (1)阻燃剂的制备：将四羟甲基硫酸磷1mol、γ-氨丙基三乙氧基硅烷0.4mol和磷酸3mol加入到三口烧瓶中，再加入三乙胺5％(四羟甲基硫酸磷和γ―氨丙基三乙氧基硅烷总重量的5％)和催化剂A为4.2g，90-120℃反应3～5h，降温到70～80℃，反应2～5h，再升温到90～100℃，加入1～2mol二乙醇胺、三氯叔丁醇0.3mol、0.3mol乙烯基膦和2-氨基异丁酸1.6g，反应时间2～6h，得到该阻燃剂；
    (2)防水剂的制备：将丙烯酸10g、三甲基羟乙基丙二胺1.6g和丙烯酸羟乙酯0.7g加入到三口瓶中，再加入引发剂A0.6g，然后加入70g水，逐步升温至85℃，依次加入22g椰油脂肪酸，16g二乙醇酰胺、三羟甲基丙烷6.9g、氨基三甲叉膦酸4.4g和四甲基乙二胺0.7g，混合均匀，升温至70℃，搅拌至完全溶解，反应2h，即得该防水剂；
    (3)向反应容器中加入以下重量配比的原料：水55～75份、乳化剂0.2～2.2份、丙烯酸0.6～3.0份，升温至50℃，搅拌30min，加入A单体，乳化时间为30～60min；升温到70℃开始通回流水，升温到75℃后保温，滴加引发剂A0.2～0.6重量份，滴加时间持续1～2h，滴加完后反应2～5h，得核层乳液；
    所述A单体是由：丙烯酸丁酯3～8重量份、甲基丙烯酸甲酯2～6重量份、丙烯酸乙酯3～3.5重量份混合而成；
    (4)向步骤(3)所得核层乳液中同时滴加B单体、0.3～0.6重量份的引发剂A和步骤(1)所得阻燃剂4.4重量份，滴加时间持续1～4h，滴加完后保温75～85℃搅拌反应2h，再加入交联剂0.5～1.0重量份，保温75～85℃反应时间1～2h，降温到50℃，加入乳化剂0.3重量份和步骤(2)所得防水剂0.7份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆；
    所述B单体是由：丙烯酸丁酯4～8重量份、甲基丙烯酸甲酯3～6重量份、丙烯酸乙酯3～5重量份混合而成。
  2. 如权利1所述的阻燃、防水、耐光水性聚氨酯涂料和胶黏剂的制备方法，其催化剂A为2,4-二氯硝基苯、对硝基苯胺、硫酸羟胺、氯化羟胺的任意一种。
  3. 如权利要求1所述的一种阻燃性核壳型水性丙烯酸酯类树脂涂料的制备方法，其特征在于，乳化剂为十二烷基苯磺酸钠与脂肪醇聚氧乙烯醚按重量比4:1混合的混合物。
  4. 如权利1所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，乙烯基膦为乙烯基膦酸二乙酯、乙烯基膦酸的任意一种。
  5. 如权利1所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，所述的引发剂A为过硫酸铵、过硫酸钾的任意一种。
  6. 如权利1所述的阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的备方法，所述的交联剂的制备方法为：将羟基乙叉二膦酸4.6g 和2-羟基丙三羧酸3.5g加入到三口烧瓶中，90℃下加入季戊四醇6.2g和三羟甲基丙烷4.1g，保温反应2～4h，再加入7-羟基香豆素-3-羧酸1.1g，于110℃下反应3-4h，得该交联剂。
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CN108912928A (zh) * 2018-06-25 2018-11-30 段小宁 阻燃、防水水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法

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CN113908821B (zh) * 2020-07-08 2024-03-19 河南润世界新型涂料科技有限公司 一种光催化复合材料的制备方法、一种环保型自清洁真石漆及其制备方法
CN115403923A (zh) * 2022-09-06 2022-11-29 董泽民 一种透明阻燃尼龙及其制备方法
CN115851065A (zh) * 2022-11-25 2023-03-28 湖北双键精细化工有限公司 一种与uv罩光面漆相配套的单组份底漆用改性丙烯酸乳液及其制备方法
CN115851065B (zh) * 2022-11-25 2023-08-15 湖北双键精细化工有限公司 一种与uv罩光面漆相配套的单组份底漆用改性丙烯酸乳液及其制备方法

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