WO2020015289A1 - 阻燃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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WO2020015289A1
WO2020015289A1 PCT/CN2018/120939 CN2018120939W WO2020015289A1 WO 2020015289 A1 WO2020015289 A1 WO 2020015289A1 CN 2018120939 W CN2018120939 W CN 2018120939W WO 2020015289 A1 WO2020015289 A1 WO 2020015289A1
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parts
flame
weight
retardant
water
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PCT/CN2018/120939
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French (fr)
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段小宁
段宝荣
张萌萌
赵玉真
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • 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

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 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 an 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.
  • 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 paint and oil-based paint are essentially different, and the properties of water-based paint and oil-based paint are also very different, it is unscientific to set water-based paint as a large branch of the paint industry. . Water-based paint and oil paint should be listed as two different series in liquid paint.
  • the self-crosslinking acrylic resin finishing agent developed by Yang Gengxu et al. In the butyl acrylate-acrylonitrile-methyl acrylate emulsion polymerization system, can be modified by introducing N-methyl methacrylamide and acrylic acid to obtain better performance.
  • Leather finishing agent can improve the leather finishing agent's resistance to organic solvents and other problems.
  • Luan Shifang et al. Prepared an acrylic acid monopolyethylene glycol monomer with long polar side groups by reacting acrylic acid with phosphoryl trichloride and halogenating it with polyethylene glycol.
  • the acrylic resin emulsion was prepared by copolymerization of acrylate and vinyl compounds. Due to the presence of long, soft polar side groups, the resin film has high tensile strength and elongation at break; it can significantly improve the coating for leather finishing The layer is resistant to solvents and water.
  • Core-shell emulsion polymerization is a new technology developed in the 1980s. It is a new resin polymerization technology based on the principle of particle design.
  • the core-shell acrylic emulsion copolymer is composed of two or more polymers in the latex particles in heterogeneous coexistence, that is, one kind of polymer is a core, the other is a core-shell, and an emulsified layer is coated outside the shell.
  • the obtained emulsion has good anti-rebound viscosity, low film forming temperature, the best film forming property, stability, and better mechanical properties, and the emulsion is provided by selecting different performance monomers as the shell layer or the core layer of the latex particles, respectively.
  • the core-shell structure can solve the problems of previous resin properties such as soft and hard, heat resistance and cold resistance one by one. This technology has been widely used in the research of acrylic resin synthesis and modification.
  • the currently used water-based acrylic resin coatings also increasingly show their insurmountable disadvantages [7] , such as slow drying and difficult film formation under low temperature and humidity conditions; the coating film is prone to mold, easy to contaminate, and is not wear-resistant ; The freeze-thaw stability and mechanical stability are not good; the dry and wet rub resistance, film-forming density, flatness, and gloss of the coating agent are not good, which limits the further improvement of the performance of the coating material.
  • the invention relates to a self-flammable acrylic emulsion, which is characterized in that: the self-flammable modified styrene-acrylic emulsion is a reactive halogen-containing flame-retardant vinyl monomer, which can be used with acrylic ester monomers. Emulsion copolymerization reaction occurs, the flame-retardant group is fixed on the molecular structure of the resin by chemical bonding, and it will not be detached.
  • the synthesized acrylic emulsion has self-flame retardant properties, and it is not necessary to add other flame retardants when preparing coatings. It can have long-lasting flame retardant performance; the invention also provides a method for preparing a self-flammable acrylic emulsion.
  • the self-fire-retardant acrylic emulsion prepared by the invention has good adhesion, water resistance and durability, and the coating film produced has water resistance, alkali resistance, scrub resistance, and long-lasting self-flame resistance, and is widely used indoors. Flame retardant coatings for outer woodware, steel structures, and constructions both play a decorative and protective role.
  • 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 amino Resin, 3-6 parts ethyl acrylate, 3-5 parts butyl acrylate, 2-10 parts melamine, 1-2 parts defoamer, 2-6 parts pigment and filler, 2-3 parts acrylic acid, 60-70 parts by weight Carboxyl-containing anionic water-based resin, 5 to 10 parts by weight of water-resistant pigments, 7 to 8 parts by weight of 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 Parts of deionized water; interfacial adhesion promoters are formed by the reaction of metal organics, polyisocyanates, and oligomers containing hydroxyl groups.
  • 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.
  • the invention relates to a method for preparing a flame-retardant water-based core-shell acrylic resin coating and paint.
  • the main synthetic route is to functionalize the cross-linking agent to improve the flame resistance of the water-based core-shell acrylic resin coating and paint.
  • Properties that is, flame retardant modification from the perspective of the chemical materials required for acrylic resins, and at the same time, due to the current anionic and non-ionic combination required for the synthesis of acrylic resins to improve the stability of acid and alkali salts and mechanical stirring Stability, combining the two into one, making a new type of emulsifier with both anionic and non-ionic properties.
  • the emulsifier can have the advantages of convenient operation, strong stability of acid and alkali salts, and strong stability of mechanical stirring.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 2 to 7 parts by weight of butyl acrylate, 2 to 5 parts by weight of methyl methacrylate, 3 to 3.5 parts by weight of ethyl acrylate, and 2-4 parts of hydroxyethyl acrylate;
  • step (2) Add monomer B and 0.3-0.4 parts by weight of initiator A to the core layer emulsion obtained in step (1) at the same time, and the dropping time lasts 1 to 2 hours. After the dropping, the temperature is kept at 75 to 85 ° C and the reaction is stirred for 3 hours. Then add 0.6 ⁇ 1.1 parts by weight of flame retardant cross-linking agent, hold at 75 ⁇ 95 °C for 1 ⁇ 3h, cool down to 50 °C, add 0.3 parts by weight of emulsifier, 30min for reaction time, add ammonia to adjust pH to 7 ⁇ 8 To obtain the flame-retardant and waterproof water-based core-shell acrylic resin coatings and paints;
  • the B monomer is a mixture of 1 to 6 parts by weight of butyl acrylate, 3 to 7 parts by weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2 to 6 parts of hydroxyethyl acrylate.
  • Initiator A is any of ammonium persulfate, potassium persulfate, and potassium persulfate; the preparation method of the emulsifier is to take 15g of triethylenetetramine and 70g of water into a three-necked flask, and slowly add the ring after heating to 30 ° C 40 g of oxyethane and 1.2 to 2.4 g of substance A, after reacting at 30 ° C for 2 hours, cooling to 25 ° C to obtain an intermediate product, and then adding 15 g of dodecylphenol and 1.6 g of m-pentadecylphenol and the substance B0.3g, then raise the temperature to 100 ° C and reflux for 1h.
  • the solvent is distilled off under reduced pressure, which is the emulsifier;
  • the substance A is ethyl 2-bromobutyrate, 9-fluorenylmethyl chloroformate, trimethyl Any one of cyclotriboroxane;
  • Substance B is any one of ethoxyamine hydrochloride, methylethylamine, and acetate propionic anhydride;
  • a method for preparing a flame-retardant crosslinking agent is: hydroxyethylidene diphosphine 2.1 g of acid, 2.5 g of tetramethylol phosphate sulfate and 1.2 g of substance C were added to 250 ml of a three-necked flask, and reacted at 70 ° C for 1 hour.
  • the flame retardant function of the cross-linking agent is used to improve the flame retardance of water-based core-shell acrylic resin coatings and paints, that is, to modify the flame retardance from the perspective of chemical materials required for acrylic resins.
  • the two due to the current combination of anionic and nonionics required for the synthesis of acrylic resins to improve the stability of acid and alkali salts and the stability of mechanical agitation, the two are combined into one, and a new type of both anionic and nonionic properties is produced.
  • Emulsifier which has the advantages of convenient operation, strong stability of acid and alkali salts, and strong stability of mechanical stirring.
  • the mechanism of the present invention is to use a cross-linking agent to make the acrylic resin form a dense film, and at the same time, there is a flame retardant group on the surface of the acrylic resin, which reduces the flame burning speed and improves its flame retardancy.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 2 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
  • step (2) To the core layer emulsion obtained in step (1), simultaneously dropwise add B monomer and 0.3 parts by weight of ammonium persulfate (dissolved in 5 g of water), and the dropping time lasts for 1 hour. After the dropping, the temperature is kept at 75 ° C. and the reaction is stirred for 3 hours. Then, add 0.6 parts by weight of flame retardant cross-linking agent, hold at 75 ° C for 1h, reduce the temperature to 50 ° C, add 0.3 parts by weight of emulsifier, 30min for reaction time, add ammonia water to adjust the pH to 7-8, and get the above mentioned resistance. Flammable core-shell acrylic resin coatings and paints;
  • the B monomer is prepared by mixing 1 part by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate.
  • the preparation method of the emulsifier is to take 15g of triethylenetetramine and 70g of water into a three-necked flask, and then slowly add 40g of ethylene oxide and 1.2g of ethyl 2-bromobutyrate after heating to 30 ° C, and react at 30 ° C for 2h. Then, it was cooled to 25 ° C to obtain an intermediate product, and then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of ethoxyamine hydrochloride were added, and the temperature was raised to 100 ° C under reflux for 1h. , Distilling off the solvent under reduced pressure is an emulsifier;
  • the flame retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylol phosphate sulfate and 1.2 g of 4,4′-bipyridine to 250 ml of a three-necked flask, and reacting at 70 ° C. for 1 h. Then, 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the mixture was reacted at 65 ° C for 1.5 h to obtain the flame-retardant crosslinking agent.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 7 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 3.5 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
  • the B monomer is a mixture of 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts of hydroxyethyl acrylate.
  • An emulsifier is prepared by taking 15g of triethylenetetramine and 70g of water into a three-necked flask, and then slowly adding 40g of ethylene oxide and 2.4g of 9-fluorenyl methyl chloroformate after heating to 30 ° C, at 30 ° C After 2 hours of reaction, it was cooled to 25 ° C to obtain an intermediate product, and then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of methyl ethylamine were added, and the temperature was raised to 100 ° C under reflux for 1h. The solvent is distilled off under reduced pressure, which is an emulsifier.
  • the flame retardant crosslinking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylol phosphate sulfate and 1.2 g of aminoacetonitrile to 250 ml of a three-necked flask. The reaction was carried out at 70 ° C. for 1 h, and then 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the reaction was performed at 65 ° C. for 1.5 h to obtain the flame-retardant crosslinking agent.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 4.5 parts by weight of butyl acrylate, 3.5 parts by weight of methyl methacrylate, 3.3 parts by weight of ethyl acrylate, and 3 parts of hydroxyethyl acrylate;
  • step (2) To the core layer emulsion obtained in step (1), dropwise add B monomer and 0.3 parts by weight of potassium persulfate (dissolved in 5 g of water) simultaneously, and the dropwise addition lasts for 1.5 hours. After 3 hours of reaction, 0.8 parts by weight of flame retardant cross-linking agent was added, the reaction time was maintained at 85 ° C for 2 hours, the temperature was lowered to 50 ° C, 0.3 parts by weight of emulsifier was added, the reaction time was 30 minutes, and the pH was adjusted to 7 to 8 by adding ammonia water. Flame-retardant water-based core-shell acrylic resin coatings and paints;
  • the B monomer is formed by mixing 3.5 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate.
  • the preparation method of the emulsifier is to take 15g of triethylenetetramine and 70g of water into a three-necked flask, and then slowly add 40g of ethylene oxide and 1.8g of trimethylcyclotriboroxane after heating to 30 ° C, and react at 30 ° C. After 2h, cool to 25 ° C to obtain an intermediate product, then add 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of acetic acid propionic anhydride, raise the temperature to 100 ° C and reflux for 1h, then reduce the pressure The solvent is distilled off, which is an emulsifier.
  • the preparation method of the flame retardant cross-linking agent is: Add 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylol phosphate sulfate and 1.2 g of iminodiacetonitrile to 250 ml of a three-necked flask. The reaction was carried out at 70 ° C. for 1 h, and then 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the reaction was performed at 65 ° C. for 1.5 h to obtain the flame-retardant crosslinking agent.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is a mixture of 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
  • step (2) To the core layer emulsion obtained in step (1), simultaneously dropwise add B monomer and 0.3 parts by weight of ammonium persulfate (dissolved in 5 g of water), and the dropping time lasts for 1 hour. After the dropping, the temperature is kept at 75 ° C. and the reaction is stirred for 3 hours.
  • the B monomer is composed of: 3 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 6 parts of hydroxyethyl acrylate Blended.
  • the preparation method of the emulsifier is to take 15g of triethylenetetramine and 70g of water into a three-necked flask, and then slowly add 40g of ethylene oxide and 1.6g of ethyl 2-bromobutyrate after heating to 30 ° C, and react at 30 ° C for 2h. Then, it was cooled to 25 ° C to obtain an intermediate product, and then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of ethoxyamine hydrochloride were added, and the temperature was raised to 100 ° C under reflux for 1h. The solvent is distilled off under reduced pressure, which is an emulsifier.
  • the preparation method of the flame-retardant cross-linking agent is: Add 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylol phosphate sulfate and 1.2 g of aminoacetonitrile to 250 ml of a three-necked flask. The reaction was carried out at 70 ° C. for 1 h, 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the reaction was conducted at 65 ° C. for 1.5 h to obtain the flame-retardant crosslinking agent.
  • Preparation method of flame-retardant water-based core-shell acrylic resin coating and paint is as follows:
  • the A monomer is made by mixing 7 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
  • step (2) To the core layer emulsion obtained in step (1), simultaneously dropwise add B monomer and 0.3 parts by weight of potassium persulfate (dissolved in 5 g of water) for a period of 1 h. After the dropwise addition, the temperature is kept at 75 ° C. and the reaction is stirred for 3 h. Then, add 0.6 parts by weight of flame retardant cross-linking agent, hold at 75 ° C for 1h, reduce the temperature to 50 ° C, add 0.3 parts by weight of emulsifier, 30min for reaction time, add ammonia water to adjust the pH to 7-8, and get the above mentioned resistance.
  • the B monomer is composed of 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts of hydroxyethyl acrylate Blended.
  • An emulsifier is prepared by taking 15 g of triethylenetetramine and 70 g of water into a three-necked flask, and then slowly adding 40 g of ethylene oxide and 1.6 g of 9-fluorenyl methyl chloroformate after heating to 30 ° C, at 30 ° C. After 2 hours of reaction, it was cooled to 25 ° C to obtain an intermediate product, and then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of methyl ethylamine were added, and the temperature was raised to 100 ° C under reflux for 1h. The solvent is distilled off under reduced pressure, which is an emulsifier.
  • the preparation method of the flame-retardant cross-linking agent is: 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylol phosphate sulfate, and 1.2 g of imino diacetonitrile are added to a three-necked flask. In 250 ml, react at 70 ° C for 1 hour, then add 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid, and react at 65 ° C for 1.5 hours to obtain the flame-retardant crosslinking agent.
  • Flame retardancy is measured by the oxygen index and flame burning time.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Oxygen Index/% 29.4 29.6 30.4 29.8 29.8 When flames burn 1.1 1.6 0.8 1.2 2.1
  • the oxygen index of the flame-retardant water-based core-shell acrylic resin coatings and paints when the flame-retardant cross-linking agent is not added with the substance C is significantly higher than that without the flame-retardant cross-linking agent.
  • the flame burning time decreased significantly.

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Abstract

阻燃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：向反应容器中加入以下重量配比的原料：水50～65份、乳化剂0.4～2.3份、甲基丙烯酸0.6～3.0份和丙烯酸0.3～0.7份，升温至45℃，搅拌40min，加入A单体，乳化时间为30～70min；升温到65℃开始通回流水，升温到77℃后保温，滴加引发剂A0.3～0.7重量份，滴加时间持续1～3h，滴加完后反应2～4h，得核层乳液；向所得核层乳液中同时滴加B单体、0.3～0.4重量份的引发剂A，滴加时间持续1～2h，滴加完后保温75～85℃搅拌反应3h，再加入阻燃***联剂0.6～1.1重量份，保温75～95℃反应时间1～3h，降温到50℃，加入乳化剂0.3重量份，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，所得阻燃性水性核壳型丙烯酸酯类树脂涂料和油漆具有良好的阻燃性。

Description

阻燃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，尤其是阻燃性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。
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。水性漆与油(性)漆应并列为液体涂料中两大不同系列。
在将丙烯酸树脂应用于皮革涂饰剂初期，人们针对其放水性、热黏、冷脆、不耐溶剂等缺点，利用了接技、交联等高分子合成技术，引入附有功能基团苯乙烯、丙烯腈等进行改性，满足皮革涂饰先天性能不足的需要，也为现代高性能皮革的研究建立了基础。
杨更须等人研制的自交联型丙烯酸树脂涂饰剂在丙烯酸丁酯－丙烯腈－丙烯酸甲酯乳液聚合体系中，通过引入N－羟甲基丙烯酰胺和丙烯酸改性，可以得到性能比较好的皮革涂饰剂，可以提高皮革涂饰剂不耐有机溶剂等问题。
栾世方等人将丙烯酸单体经三氯化磷酰卤化后，与聚乙二醇反应制备了一种含长极性侧基的丙烯酸单聚乙二醇酯单体，然后将该单体和其它丙烯酸酯、乙烯基类化合物共聚制备了丙烯酸树脂乳液，由于长的、柔软极性侧基的存在，该树脂膜具有较高的抗张强度、断裂伸长率；用于皮革涂饰可明显提高涂层的耐溶剂及耐水性能。核-壳乳液聚合是80年代发展起来的一种新技术，它是一种以粒子设计原理进行的全新的树脂聚合技术。核壳型丙烯酸类乳液共聚物由两种以上聚合物呈非均相共存于乳胶粒中，即一种聚合物为核芯，另一种为核壳，壳外再包乳化层。得到的乳液抗回粘性好、成膜温度低,最好的成膜性、稳定性以 及更优越的力学性能,并通过选择不同性能单体分别作为乳胶粒的壳层或核层从而使乳液具有特定性能，核壳结构可使以往树脂性能的问题如软与硬、耐热与耐寒等问题逐一解决，此技术已广泛应用于丙烯酸树脂的合成与改性研究中。
但目前使用的水乳型丙烯酸树脂涂料也日益表现出其不可克服的缺点 [7]，如在低温多湿的情况下，干燥慢，难以成膜；涂膜易生霉，易污染，不耐磨；冻融稳定性和机械稳定性不好；涂饰剂的耐干湿擦性、成膜致密性、平整性及光泽性不好等，使涂饰材料性能的进一步提高受到限制。
此外存在阻燃性能不高和加入乳化剂比较繁琐的缺陷。
201610506501.6本发明涉及一种自阻燃型丙烯酸乳液，其特征在于：所述的自阻燃型改性苯丙乳液，是利用反应型含卤阻燃型乙烯基单体，可与丙烯酸酯类单体发生乳液共聚合反应，通过化学键方式把阻燃基团固定在树脂分子结构上，不会解析脱落，合成后的丙烯酸乳液具有自阻燃性能，制备涂料时不需要另外添加其它阻燃剂就可起到持久阻燃性能；本发明还提供一种自阻燃型丙烯酸乳液的制备方法。本发明制得的自阻燃型丙烯酸乳液具有良好的附着力、耐水性，耐久性，制成的涂膜具有耐水性、耐碱性、耐擦洗性和持久自阻燃性能，广泛用于室内外木器、钢结构、建筑的阻燃涂料，既起到装饰作用，又起到保护作用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。
发明内容
本发明涉及到阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，主要的合成路线是将交联剂阻燃功能化来提高水性核壳型丙烯酸酯类树脂涂料和油漆的阻燃性，也就是从涉及到丙烯酸酯类树脂所需化工材料的角度进行阻燃改性，同时由于目前丙烯酸酯类树脂的合成中所需阴离子和非离子搭配提高酸碱盐稳定性和机械搅拌得稳定性，将二者合二为一，自制一种新型兼有阴离子和非离子性能的乳化剂，该乳化剂可具有操作方便，酸碱盐稳定性和机械搅拌得稳定性强的优势。
阻燃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)向反应容器中加入以下重量配比的原料：水50～65份、乳化剂0.4～2.3份、甲基丙烯酸0.6～3.0份和丙烯酸0.3～0.7份，升温至45℃，搅拌40min，加入A单体，乳化时间为30～70min；升温到65℃开始通回流水，升温到77℃后保温，滴加引发剂A0.3～0.7重量份，滴加时间持续1～3h，滴加完后反应2～4h，得核层乳液；
所述A单体是由：丙烯酸丁酯2～7重量份、甲基丙烯酸甲酯2～5重量份、丙烯酸乙酯3～3.5重量份、丙烯酸羟乙酯2-4份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.3～0.4重量份的引发剂A，滴加时间持续1～2h，滴加完后保温75～85℃搅拌反应3h，再加入阻燃***联剂0.6～1.1重量份，保温75～95℃反应时间1～3h，降温到50℃，加入乳化剂0.3重量份，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1～6重量份、甲基丙烯酸甲酯3～7重量份、丙烯酸乙酯3～5重量份、丙烯酸羟乙酯2-6份混合而成。
引发剂A为过硫酸铵、过硫酸钾、过硫酸氢钾的任意一种；乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和物质A1.2～2.4g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和物质B0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；物质A为2-溴丁酸乙酯、9-芴甲基氯甲酸酯、三甲基环三硼氧烷的任意一种；物质B为乙氧基胺盐酸盐、甲基乙胺和乙酸丙酸酐的任意一种；阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和物质C1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂；物质C为4,4'-联吡啶、氨基乙腈、亚氨基二乙腈的任意一种。
本发明的优势在于：
(1)将交联剂阻燃功能化来提高水性核壳型丙烯酸酯类树脂涂料和油漆的阻燃性，也就是从涉及到丙烯酸酯类树脂所需化工材料的角度进行阻燃改性，同时由于目前丙烯酸酯类树脂的合成中所需阴离子和非离子搭配提高酸碱盐稳定性和机械搅拌得稳定性，将二者合二为一，自制一种新型兼有阴离子和非离子性能的乳化剂，该乳化剂可具有操作方便，酸碱盐稳定性和机械搅拌得稳定性强的优势。
(2)2-溴丁酸乙酯、9-芴甲基氯甲酸酯、三甲基环三硼氧烷作为乳化剂合成催化剂，而采用乙氧基胺盐酸盐、甲基乙胺和乙酸丙酸酐来提高十二烷基苯酚、间十五烷基酚的协效剂；4,4'-联吡啶、氨基乙腈、亚氨基二乙腈作为羟基乙叉二膦酸、四羟甲基硫酸磷的催化剂。
(3)本发明的机理在于采用交联剂使丙烯酸酯类树脂形成致密的膜，同时在丙烯酸酯类树脂表面有阻燃集团，降低了火焰的燃烧速度，提高了其阻燃性。
具体实施方式
实例1
阻燃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)向反应容器中加入以下重量配比的原料：将水50份、乳化剂0.4份、甲基丙烯酸0.6份和丙烯酸0.3份加入到反应容器中，升温至45℃，搅拌40min，加入A单体，乳化时间为30min；升温到65℃开始通回流水，升温到77℃后保温，滴加过硫酸铵0.3重量份(用5g水溶解)，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2重量份、甲基丙烯酸甲酯2重量份、丙烯酸乙酯3重量份、丙烯酸羟乙酯2份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.3重量份的过硫酸铵(用5g水溶解)，滴加时间持续1h，滴加完后保温75℃搅拌反应3h，再加入阻燃***联剂0.6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，反应时间30min，加氨水调pH值至7～8，得所述的阻燃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1重量份、甲基丙烯酸甲酯3重量份、丙烯酸乙酯3重量份、丙烯酸羟乙酯2份混合而成。
乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和2-溴丁酸乙酯1.2g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和乙氧基胺盐酸盐0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；
阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和4,4'-联吡啶1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
实例2
阻燃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)向反应容器中加入以下重量配比的原料：将水65份、乳化剂2.3份、甲基丙烯酸3.0份和丙烯酸0.7份，升温至45℃，搅拌40min，加入A单体，乳化时间为70min；升温到65℃开始通回流水，升温到77℃后保温，滴加过硫酸钾0.7重量份(用5g水溶解)，滴加时间持续3h，滴加完后反应4h，得核层乳液；
所述A单体是由：丙烯酸丁酯7重量份、甲基丙烯酸甲酯5重量份、丙烯酸乙酯3.5重量份、丙烯酸羟乙酯4份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.4重量份的过硫酸钾(用5g水溶解)，滴加时间持续2h，滴加完后保温85℃搅拌反应3h，再加入阻燃***联剂1.1重量份，保温95℃反应时间3h，降温到50℃，加入乳化剂0.3重量份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃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7重量份、丙烯酸乙酯5重量份、丙烯酸羟乙酯6份混合而成。
乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和9-芴甲基氯甲酸酯2.4g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和甲基乙胺0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和氨基乙腈1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
实例3
阻燃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)向反应容器中加入以下重量配比的原料：将水57份、乳化剂1.3份、甲基丙烯酸1.8份和丙烯酸0.5份，升温至45℃，搅拌40min，加入A单体，乳化时间为50min；升温到65℃开始通回流水，升温到77℃后保温，滴加过硫酸氢钾0.5重量份(用5g水溶解)，滴加时间持续2h，滴加完后反应3h，得核层乳液；
所述A单体是由：丙烯酸丁酯4.5重量份、甲基丙烯酸甲酯3.5重量份、丙烯酸乙酯3.3重量份、丙烯酸羟乙酯3份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.3重量份的过硫酸氢钾(用5g水溶解)，滴加时间持续1.5h，滴加完后保温80℃搅拌反应3h，再加入阻燃***联剂0.8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，反应时间30min，加氨水调pH值至7～8，得所述的阻燃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3.5重量份、甲基丙烯酸甲酯5重量份、丙烯酸乙酯4重量份、丙烯酸羟乙酯4份混合而成。
乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和三甲基环三硼氧烷1.8g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和乙酸丙酸酐0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和亚氨基二乙腈1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
实例4
阻燃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)向反应容器中加入以下重量配比的原料：水50份、乳化剂2.3份、甲基丙烯酸3.0份和丙烯酸0.3份，升温至45℃，搅拌40min，加入A单体，乳化时间为40min；升温到65℃开始通回流水，升温到77℃后保温，滴加过硫酸铵0.4重量份(用5g水溶解)，滴加时间持续1.5h，滴加完后反应3h，得核层乳液；
所述A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、丙烯酸羟乙酯4份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.3重量份的过硫酸铵(用5g水溶解)，滴加时间持续1h，滴加完后保温75℃搅拌反应3h，再加入阻燃***联剂0.7重量份，保温80℃反应时间2h，降温到50℃，加入乳化剂0.3重量份，反应时间30min，加氨水调pH值至7～8，得所述的阻燃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3重量份、甲基丙烯酸甲酯4重量份、丙烯酸乙酯4重量份、丙烯酸羟乙酯6份混合而成。
乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和2-溴丁酸乙酯1.6g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和乙氧基胺盐酸盐0.3g，再升 高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和氨基乙腈1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
实例5
阻燃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)向反应容器中加入以下重量配比的原料：将水65份、乳化剂2.3份、甲基丙烯酸3.0份和丙烯酸0.7份，升温至45℃，搅拌40min，加入A单体，乳化时间为70min；升温到65℃开始通回流水，升温到77℃后保温，滴加过硫酸钾0.7重量份(用5g水溶解)，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7重量份、甲基丙烯酸甲酯4重量份、丙烯酸乙酯3重量份、丙烯酸羟乙酯2份混合而成；
(2)向步骤(1)所得核层乳液中同时滴加B单体、0.3重量份的过硫酸钾(用5g水溶解)，滴加时间持续1h，滴加完后保温75℃搅拌反应3h，再加入阻燃***联剂0.6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，反应时间30min，加氨水调pH值至7～8，得所述的阻燃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7重量份、丙烯酸乙酯5重量份、丙烯酸羟乙酯6份混合而成。
乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和9-芴甲基氯甲酸酯1.6g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和甲基乙胺0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂；阻燃***联剂的制备方法为；将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和亚氨基二乙腈1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
阻燃性通过氧指数、有焰燃烧时间来衡量。
表1测试性能
  实例1 实例2 实例3 实例4 实例5
氧指数/％ 29.4 29.6 30.4 29.8 29.8
有焰燃烧时 1.1 1.6 0.8 1.2 2.1
间/s          
从表1可以看出，阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的氧指数大幅提高，而有焰燃烧时间大幅降低，而对比201610506501.6和201610645798.4的实例1的氧指数和有焰燃烧时间分别为22.6，26.5s和24.1和36.5s。
表2测试性能(未加阻燃交联剂)
Figure PCTCN2018120939-appb-000001
从表2可以看出，未加阻燃交联剂阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的氧指数大幅降低，而有焰燃烧时间大幅提高。
表3测试性能(加阻燃交联剂，未加物质C)
Figure PCTCN2018120939-appb-000002
从表3可以看出，加阻燃交联剂未加物质C时的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的氧指数相比未加阻燃交联剂大幅升高，而有焰燃烧时间大幅下降。
表4测试性能(加阻燃交联剂，加物质C，未加2,3-吡啶二羧酸)
Figure PCTCN2018120939-appb-000003
从表4可以看出，加阻燃交联剂、加物质C，而未加2,3-吡啶二羧酸时的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的氧指数相比未加阻燃交联剂大幅升高，而有焰燃烧时间大幅下降。
耐化学试剂稳定性:分别将乳液与5％氯化钠溶液按体积比1:4的比例混合，密封并静置48h，观察其沉淀量。
凝胶率：测量丙烯酸树脂合成中的凝胶的重量与理论所得乳液的重量的百分比。
表5乳液稳定性数据
Figure PCTCN2018120939-appb-000004
从表5可以发现，本发明的耐化学稳定性和凝胶滤都比较好。，对比样的201610506501.6和201610645798.4的实例1的凝胶滤分别为9.7％和8.3％。
表6乳液稳定性数据(未加物质A)
Figure PCTCN2018120939-appb-000005
从表6可以发现，未加物质A的本发明的耐化学稳定性和凝胶滤显著下降。
表7乳液稳定性数据(加物质A，没有加物质B)
Figure PCTCN2018120939-appb-000006
从表7可以发现，本发明未加物质B的凝胶和耐化学稳定性显著下降。

Claims (7)

  1. 阻燃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)向反应容器中加入以下重量配比的原料：将水50～65份、乳化剂0.4～2.3份、甲基丙烯酸0.6～3.0份和丙烯酸0.3～0.7份混合搅拌，升温至45℃，搅拌40min，加入A单体，乳化时间为30～70min；升温到65℃开始通回流水，升温到77℃后保温，滴加引发剂A0.3～0.7重量份，滴加时间持续1～3h，滴加完后反应2～4h，得核层乳液；
    所述A单体是由：丙烯酸丁酯2～7重量份、甲基丙烯酸甲酯2～5重量份、丙烯酸乙酯3～3.5重量份、丙烯酸羟乙酯2-4份混合而成；
    (2)向步骤(1)所得核层乳液中同时滴加B单体、0.3～0.4重量份的引发剂A，滴加时间持续1～2h，滴加完后保温75～85℃搅拌反应3h，再加入阻燃***联剂0.6～1.1重量份，保温75～95℃反应时间1～3h，降温到50℃，加入乳化剂0.3重量份，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1～6重量份、甲基丙烯酸甲酯3～7重量份、丙烯酸乙酯3～5重量份、丙烯酸羟乙酯2-6份混合而成。
  2. 如权利1所述的阻燃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、过硫酸氢钾的任意一种。
  3. 如权利1所述的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，所述的乳化剂的制备方法为取15g三乙烯四胺、70g水加入到三口烧瓶中，升温至30℃后缓慢加入环氧乙烷40g和物质A1.2～2.4g，在30℃下反应2h后，冷却到25℃，得到中间产物，然后加入15g的十二烷基苯酚、1.6g间十五烷基酚和物质B0.3g，再升高温度到100℃回流反应1h，减压蒸馏出溶剂，即为乳化剂。
  4. 如权利3所述的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，物质A为2-溴丁酸乙酯、9-芴甲基氯甲酸酯、三甲基环三硼氧烷的任意一种。
  5. 如权利3所述的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，物质B为乙氧基胺盐酸盐、甲基乙胺和乙酸丙酸酐的任意一种。
  6. 如权利1所述的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法，所述的阻燃***联剂的制备方法为：将羟基乙叉二膦酸2.1g、四羟甲基硫酸磷2.5g和物质C1.2g加入到三口烧瓶250ml中，70℃下反应1h，再加入甲酰胺1.5g和2,3-吡啶二羧酸1.6g，65℃下反应1.5h,得该阻燃***联剂。
  7. 如权利6所述的阻燃水性核壳型丙烯酸酯类树脂涂料和油漆的制备方法,物质C为4,4'-联吡啶、氨基乙腈、亚氨基二乙腈的任意一种。
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