WO2022142000A1 - 高阻隔和高耐水的水性丙烯酸乳液及其制备方法 - Google Patents

高阻隔和高耐水的水性丙烯酸乳液及其制备方法 Download PDF

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WO2022142000A1
WO2022142000A1 PCT/CN2021/090134 CN2021090134W WO2022142000A1 WO 2022142000 A1 WO2022142000 A1 WO 2022142000A1 CN 2021090134 W CN2021090134 W CN 2021090134W WO 2022142000 A1 WO2022142000 A1 WO 2022142000A1
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water
acrylic emulsion
based acrylic
emulsion
acrylate
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PCT/CN2021/090134
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English (en)
French (fr)
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朱清梅
黄宏存
陈新生
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海南必凯水性新材料有限公司
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Priority to CA3130962A priority Critical patent/CA3130962C/en
Publication of WO2022142000A1 publication Critical patent/WO2022142000A1/zh

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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of coatings, in particular to a water-based acrylic emulsion with high barrier and high water resistance and a preparation method thereof.
  • Formaldehyde is one of the main pollutants in indoor air. Newly renovated houses and new furniture are often accompanied by the release of formaldehyde. Its release is a long-term process. Free formaldehyde in the air will cause great harm to human health and the environment. .
  • the technical problem solved by the present invention is to provide an aqueous acrylic emulsion, which has good barrier properties to formaldehyde, can reduce the amount of formaldehyde released, and at the same time the emulsion has excellent water resistance.
  • the emulsion itself is a pure water-based material, which is environmentally friendly, non-toxic, and has no irritating odor.
  • the present application provides a high-barrier and high-water-resistant water-based acrylic emulsion prepared from the following raw materials:
  • the acrylate mixture includes N-aminoacrylamide, methyl methacrylate, methyl acrylate and methacrylic acid;
  • Described compound emulsifier is reactive emulsifier sodium allyl hydroxyalkyl sulfonate and sodium lauryl sulfate;
  • the film-forming agent is triethylene glycol diisocaprylate
  • the wetting agent is macromolecular polyether modified polyester.
  • the acrylate mixture also includes ethyl methacrylate and ethyl acrylate.
  • the mass ratio of the methyl acrylate to the methyl methacrylate is 1:1 to 1:5.
  • the mass ratio of the reactive emulsifier SR-10 to sodium lauryl sulfate is 10:1 to 10:4.
  • the defoamer is selected from one or more of mineral oils, silicones and polyethers.
  • the preservative is selected from one or more of cassone and sodium benzoate.
  • the pH adjuster is selected from sodium bicarbonate, and the initiator is selected from potassium persulfate.
  • the application also provides the preparation method of the described water-based acrylic emulsion, comprising the following steps:
  • reaction solution b) mixing remaining soft water, methyl methacrylate, compound emulsifier, initiator and pH regulator, and reacting to obtain a reaction solution;
  • step c) The reaction solution obtained in step c) is mixed with a defoaming agent and then vacuumed, and then a preservative, a wetting agent and a film-forming agent are added to obtain an aqueous acrylic emulsion.
  • step b the temperature of the reaction is 80-90° C. and the time is 0.5-1 h; in step c), the temperature of the reaction is 80-90° C. and the time is 1-2 h.
  • step d) before vacuuming, it also includes cooling to 40-60°C.
  • the application provides an aqueous acrylic emulsion, which is prepared from the following raw materials: 10wt%-50wt% acrylate mixture; 1wt%-10wt% film-forming agent, 0.5wt%-2wt% wetting agent, 1wt% ⁇ 3wt% compound emulsifier, 0.2wt% ⁇ 0.5wt% defoamer, 0.1wt% ⁇ 0.3wt% preservative, 0.1wt% ⁇ 0.3wt% initiator, 0.1wt% ⁇ 0.2wt% 35wt% to 87wt% of soft water.
  • N-aminoacrylamide is specially added to the monomer to participate in the polymerization reaction, so that the molecular chain of the emulsion has amino and amide groups.
  • a three-dimensional network structure is formed to enhance the water resistance and film-forming hardness of the emulsion, and the amino group on the molecular chain can also react with the aldehyde group, so that the coating has the ability to absorb formaldehyde; reactive emulsifiers SR-10 and twelve
  • the compounding of sodium alkyl sulfate can effectively promote the emulsification and dispersion of each component, improve the compatibility between each component, effectively reduce the slag, and further improve the water resistance, barrier performance and stability of the emulsion;
  • the film-forming agent adopts triethylene glycol diisooctanoate, which not only has a smaller odor, but also can completely enter the polymer particles after adding the acrylic emulsion.
  • the wetting agent is a macromolecule polyether modified polyester, which is Not only has good anti-shrinkage ability, the emulsion is even and smooth during film formation, and it will also be cross-linked with the emulsion molecular chain during film formation, which further enhances the barrier performance and water resistance. Therefore, in the present application, by adding the above components and adjusting the content of the above components, the aqueous acrylic emulsion has high barrier properties and high water resistance. Further, the present application defines the ratio of methyl acrylate and methyl methacrylate, so that the emulsion can have a higher Tg value, further improve the hardness during film formation, and the emulsion has excellent barrier properties.
  • the present application provides a high-barrier and high-water-resistant water-based acrylic emulsion, which has good barrier properties to formaldehyde and can effectively reduce the amount of formaldehyde released.
  • the emulsion has excellent water resistance; the emulsion itself is a pure water-based material, which is environmentally friendly, non-toxic, non-irritating, and has a transparent coating with high hardness.
  • the embodiment of the present invention discloses a water-based acrylic emulsion with high barrier and high water resistance, which is prepared from the following raw materials:
  • the acrylate mixture includes N-aminoacrylamide, methyl methacrylate, methyl acrylate and methacrylic acid;
  • Described compound emulsifier is reactive emulsifier SR-10 and sodium lauryl sulfate;
  • the film-forming agent is triethylene glycol diisocaprylate
  • the wetting agent is macromolecular polyether modified polyester.
  • the acrylate mixture mainly affects the film thickness.
  • the mass ratio of the methyl acrylate to the methyl methacrylate is 1:1 to 1:5; more Specifically, the mass ratio of methyl acrylate and methyl methacrylate is 1:1, 1:2, 1:3, 1:4 or 1:5.
  • the N-aminoacrylamide in the above-mentioned acrylate mixture participates in the polymerization reaction, so that the molecular chain of the emulsion has amino groups and amide groups.
  • the amino groups and amide groups can not only be cross-linked during the film forming of the emulsion to form a three-dimensional network structure, which enhances the emulsion's properties.
  • Water resistance and film-forming hardness, and the amino group on the molecular chain can also react with the aldehyde group, so that the coating has the ability to absorb formaldehyde; the specific ratio of methyl acrylate and methyl methacrylate makes the emulsion can have higher
  • the Tg value can further improve the hardness of the film, and the emulsion barrier performance is excellent; methacrylic acid is a water-soluble monomer, which can enhance the adhesion and significantly improve the adhesion of the film to the substrate.
  • the acrylate mixture also includes ethyl methacrylate and ethyl acrylate; it adjusts the glass transition temperature of the polymer, and adjusts the minimum film-forming temperature and film-forming hardness of the emulsion.
  • the content of the acrylate mixture is 10-50 wt %, and more specifically, the content of the acrylate mixture is 20-40 wt %.
  • the compound emulsifier is a reactive emulsifier sodium allyl hydroxyalkyl sulfonate (reactive emulsifier SR-10) and sodium lauryl sulfate, and the mass ratio thereof is 10:1 to 10:4, more Specifically, the mass ratio of the reactive emulsifier SR-10 and sodium lauryl sulfate is 10:1, 10:2, 10:3 or 10:4;
  • the emulsification and dispersion of the emulsion improves the compatibility between the components, effectively reduces the slag, and further improves the water resistance, barrier performance and stability of the emulsion.
  • the content of the compound emulsifier is 1 to 3 wt %, and more specifically, the content of the compound emulsifier is 1 wt %, 2 wt % or 3 wt %.
  • the film-forming agent is selected from triethylene glycol diisooctanoate, which not only has a smaller odor, but also can completely enter the polymer particles after being added to the acrylic emulsion.
  • the content of the film-forming agent is 1-10 wt %, and more specifically, the content of the film-forming agent is 2-9 wt %.
  • the wetting agent is selected from macromolecular polyether modified polyester, which not only has good anti-shrinkage ability, the emulsion is even and smooth during film formation, and also cross-links with the emulsion molecular chain during film formation to further enhance the barrier. performance and water resistance.
  • the content of the wetting agent is 0.5 wt % to 2 wt %, and more specifically, the content of the wetting agent is 0.8 to 1.9 wt %.
  • the compound emulsifier, film-forming agent and wetting agent in the present application is the key to ensure that the water-based acrylic emulsion achieves high barrier and high water resistance.
  • the application also includes auxiliary agents: defoamer, preservative, initiator, pH adjuster, wherein the defoamer is selected from one or more of mineral oils, silicones and polyethers, Its content is 0.2 to 0.5wt%, more specifically, its content is 0.3wt%, 0.4wt%, 0.5wt% or 0.2wt%; the preservative is selected from one or more of cassone and sodium benzoate , its content is 0.1-0.3wt%, more specifically, its content is 0.1wt%, 0.2wt% or 0.3wt%; the pH adjuster is selected from sodium bicarbonate, and its content is 0.1-0.2wt%; The initiator is selected from potassium persulfate, and its content is 0.1-0.3 wt %, more specifically, its content is 0.1 wt %, 0.2 wt % or 0.3 wt %.
  • the defoamer is selected from one or more of mineral oils, silicones and polyethers
  • the application also provides a preparation method of the water-based acrylic emulsion, comprising the following steps:
  • reaction solution b) mixing remaining soft water, methyl methacrylate, compound emulsifier, initiator and pH regulator, and reacting to obtain a reaction solution;
  • step c) The reaction solution obtained in step c) is mixed with a defoaming agent and then vacuumed, and then a preservative, a wetting agent and a film-forming agent are added to obtain an aqueous acrylic emulsion.
  • step a) is a pre-emulsification process, that is, the reaction monomer and the reactive emulsifier are fully mixed.
  • the acrylate mixed solution also includes ethyl methacrylate and ethyl acrylate, it is also added before the compound emulsifier is added at the same time.
  • Step b) is a seed reaction stage, that is, the polymerization process of methyl methacrylate. After the raw materials are mixed, the stirring temperature is raised to 80-90° C., and the temperature is maintained for 30 minutes.
  • Step c) is the main reaction stage, and the monomer is polymerized to form a high polymer; the first mixed solution and the second mixed solution are added dropwise to the reaction solution, dripped for 3 to 5 hours, and kept for 1 to 2 hours, and the temperature during the heat preservation is 80 °C. ⁇ 90°C.
  • a defoaming agent is added, and when the temperature drops to 40-60 °C, vacuum is applied to remove residual monomers in the emulsion, effectively reducing the participation of monomers in the emulsion and reducing the smell of the emulsion. This stage lasts for 4-12 hours. Wait for the temperature When the temperature is lowered to below 40°C, preservatives, wetting agents and film-forming agents are added to obtain an aqueous acrylic emulsion.
  • the water-based acrylic emulsion provided by the invention is coated on the artificial plywood, and the coating can effectively block more than 80% of the formaldehyde release of the plywood, effectively reduce the amount of formaldehyde released, and significantly reduce the content of free formaldehyde molecules in the air; put the plywood into water Soaked for 72 hours, the coating has no whitening and swelling, and does not affect the barrier properties. It can be widely used in exterior wall coatings and wooden furniture coatings without affecting performance or appearance. At the same time, the film-forming hardness of the emulsion is high, the coating is transparent and high-gloss, and there is no irritating odor.
  • a high-barrier and high-water-resistant water-based acrylic emulsion which is prepared from the following raw materials by weight: 10% of acrylate mixture, 1% of film-forming agent, 0.5% of wetting agent, 1% of compound emulsifier, and defoamer 0.2%, preservative 0.1%, initiator 0.1%, pH adjuster 0.1%, soft water 87%;
  • acrylate mixture consists of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid , N-aminoacrylamide mixed, wherein the mixing ratio of methyl acrylate and methyl methacrylate is 1:1;
  • the compound emulsifier is the compound of reactive emulsifier SR-10 and sodium lauryl sulfate , the compounding ratio is 10:1;
  • the film-forming agent is triethylene glycol diisocaprylate;
  • the wetting agent is macromolecular polyether modified polyester;
  • a method for preparing a water-based acrylic emulsion with high barrier and high water resistance comprising the following steps:
  • step (a) Slowly add the prepared monomer and initiator solution in the step (a) dropwise into the reaction kettle, after 3h dripping, keep a constant speed during the dripping; after the dripping is completed, keep the temperature at 80°C for 1h;
  • a high-barrier and high-water-resistant water-based acrylic emulsion prepared from the following raw materials by weight: 50% of acrylate mixture, 9% of film-forming agent, 2% of wetting agent, 3% of compound emulsifier, defoamer 0.3%, preservative 0.3%, initiator 0.3%, pH adjuster 0.1%, soft water 35%;
  • acrylate mixture consists of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid , N-aminoacrylamide mixed, wherein the mixing ratio of methyl acrylate and methyl methacrylate is 1:5;
  • the compound emulsifier is the compound of reactive emulsifier SR-10 and sodium lauryl sulfate , the compounding ratio is 10:4;
  • the film-forming agent is triethylene glycol diisooctanoate;
  • the wetting agent is macromolecular polyether modified polyester;
  • a method for preparing a water-based acrylic emulsion with high barrier and high water resistance comprising the following steps:
  • step (a) Slowly add the prepared monomer and initiator solution in step (a) dropwise into the reaction kettle, after 5h dripping, keep a constant speed during dripping; after dripping, keep warm for 2h, and keep the temperature at 90°C;
  • a high-barrier and high-water-resistant water-based acrylic emulsion which is prepared from the following raw materials by weight: 40% of acrylate mixture, 10% of film-forming agent, 1.9% of wetting agent, 2% of compound emulsifier, and defoamer 0.5%, preservative 0.2%, initiator 0.2%, pH adjuster 0.2%, soft water 45%;
  • acrylate mixture consists of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid , N-aminoacrylamide mixed, wherein the mixing ratio of methyl acrylate and methyl methacrylate is 1:3;
  • the compound emulsifier is the compound of reactive emulsifier SR-10 and sodium lauryl sulfate , the compounding ratio is 10:2;
  • the film-forming agent is triethylene glycol diisooctanoate;
  • the wetting agent is macromolecular polyether modified polyester;
  • a method for preparing a water-based acrylic emulsion with high barrier and high water resistance comprising the following steps:
  • step (a) Slowly add the prepared monomer and initiator solution in step (a) dropwise into the reaction kettle, after 3.3h dripping, keep a constant speed during dripping; after dripping, keep warm for 1.6h, and keep the temperature at 84°C ;
  • the acrylate mixture in Example 1 is obtained by mixing methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, and N-aminoacrylamide, wherein methyl acrylate and methacrylic acid are mixed.
  • the mixing ratio of methyl ester is 1:1, replaced by: the acrylate mixture is obtained by mixing methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and methacrylic acid, wherein methyl acrylate and methyl acrylate are mixed.
  • the mixing ratio of methyl methacrylate is 1:7, and other formulas and preparation methods remain unchanged.
  • the film-forming agent in the embodiment 2 is triethylene glycol diisooctanoate, and the wetting agent is a macromolecular polyether-modified polyester, and is replaced by: the film-forming agent is dipropylene glycol methyl ether, and the wetting agent is Glide 496 , the rest of the formula and preparation method remain unchanged.
  • the artificial plywood coated with the water-based acrylic emulsion prepared in Examples 1 to 3 has a low formaldehyde release concentration, and the acrylic emulsion can effectively block formaldehyde release; Good; the emulsion film is transparent and high gloss, without irritating odor.
  • the artificial plywood coated with the water-based acrylic emulsion prepared in Comparative Examples 1 to 2 has a high formaldehyde emission concentration, and the plywood appears white and has a pungent odor after soaking in water for a period of time.
  • N-aminoacrylamide is specially added to the monomer to participate in the polymerization reaction, so that the molecular chain of the emulsion has amino and amide groups.
  • a three-dimensional network structure is formed to enhance the water resistance and film-forming hardness of the emulsion, and the amino group on the molecular chain can also react with the aldehyde group, so that the coating has the ability to absorb formaldehyde; by limiting methyl acrylate and methyl methacrylate
  • the mixing ratio of the emulsion can have a higher Tg value, further improve the hardness during film formation, and the emulsion barrier performance is excellent; the use of reactive emulsifier SR-10 and sodium lauryl sulfate for compound use can effectively promote
  • the emulsification and dispersion of each component improves the compatibility between the components, effectively reduces the slag, and further improves the water resistance, barrier performance and stability of the emulsion.
  • the shelf life of the present invention can be extended from 4 months to 12 months. All the auxiliaries in the formula of the present invention will not produce a large irritating odor, and the residual monomer in the emulsion will be completely removed by vacuuming in the production process, so that a non-irritating odor can be prepared.
  • Acrylic emulsion Compared with the acrylic emulsion using a single emulsifier, The shelf life of the present invention can be extended from 4 months to 12 months. All the auxiliaries in the formula of the present invention will not produce a large irritating odor, and the residual monomer in the emulsion will be completely removed by vacuuming in the production process, so that a non-irritating odor can be prepared. Acrylic emulsion.
  • the commonly used alcohol ester and glycol ether film-forming agents in the market are water-soluble. After adding acrylic emulsion, the part will be between the water phase and the polymer phase. Therefore, a large amount of addition is required to better promote The film formation of the emulsion, and the water resistance of the emulsion will also be affected after addition.
  • the film-forming agent of the present invention adopts triethylene glycol diisooctanoate, which not only has a smaller odor, but also can completely enter the polymer particles after being added to the acrylic emulsion, so the emulsion can be effectively reduced when the addition ratio is low. The lowest film-forming temperature can promote the film-forming of the emulsion without affecting the water resistance of the emulsion itself.
  • the commonly used polyether siloxane copolymers and acetylene glycol wetting agents on the market will reduce the water resistance of the acrylic emulsion after addition, and the wetting agent used in the present invention is a macromolecular polyether modified polyester , it not only has good anti-shrinkage ability, the emulsion film is even and smooth, but also cross-links with the emulsion molecular chain during film formation, which further enhances the barrier performance and water resistance.

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Abstract

本发明提供了一种高阻隔和高耐水的水性丙烯酸乳液，包括：丙烯酸酯混合物10wt％～50wt％、成膜剂1wt％～10wt％％、润湿剂0.5wt％～2wt％、复配乳化剂1wt％～3wt％、消泡剂0.2wt％～0.5wt％、防腐剂0.1wt％～0.3wt％、引发剂0.1wt％～0.3wt％、pH调节剂0.1wt％～0.2wt％，软水35wt％～87wt％。本发明的水性丙烯酸乳液对甲醛具有良好阻隔性，可有效降低甲醛的释放量，同时乳液具有优秀的耐水性能，可广泛应用于外墙涂料、木制家具涂层上；乳液本身为纯水性材料，环保无毒，无刺激性气味，且涂层透明高光泽。

Description

高阻隔和高耐水的水性丙烯酸乳液及其制备方法
本申请要求于2020年12月28日提交中国专利局、申请号为202011577988.X、发明名称为“高阻隔和高耐水的水性丙烯酸乳液及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及涂料技术领域，尤其涉及高阻隔和高耐水的水性丙烯酸乳液及其制备方法。
背景技术
甲醛是室内空气主要污染物之一，新装修的房屋和新家具常常就伴有甲醛的释放，它的释放是一个长期的过程，空气中游离态的甲醛会对人体健康和环境产生极大的危害。
市场上关于甲醛的治理方法很多，但大多收效甚微或无法长时间使用，对于应用在外墙和新家具上的涂料，大部分由于不是完全的水性环保涂料或乳液本身有强烈刺激性气味，无法被市场接受。水性丙烯酸乳液是环境友好型涂料，其成膜透明且具有一定的光泽度和阻隔性，然而目前市场上大部分的水性丙烯酸乳液只能阻隔70％以下的甲醛释放，且乳液成膜耐水性能较差，长时间泡水容易发白影响美观，且泡水后容易脱落，因此无法被客户所接受。
发明内容
本发明解决的技术问题在于提供一种水性丙烯酸乳液，其对甲醛具有良好的阻隔性，可降低甲醛的释放量，同时乳液具有优秀的耐水性能。乳液本身为纯水性材料，环保无毒，无刺激性气味。
有鉴于此，本申请提供了一种高阻隔和高耐水的水性丙烯酸乳液，由以下原料制备得到：
Figure PCTCN2021090134-appb-000001
Figure PCTCN2021090134-appb-000002
所述丙烯酸酯混合物中包括N-氨基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯和甲基丙烯酸；
所述复配乳化剂为反应型乳化剂烯丙基羟烷基磺酸钠和十二烷基硫酸钠；
所述成膜剂为三乙二醇二异辛酸酯；
所述润湿剂为大分子聚醚改性聚酯。
优选的，所述丙烯酸酯混合物中还包括甲基丙烯酸乙酯和丙烯酸乙酯。
优选的，所述丙烯酸酯混合物中，所述丙烯酸甲酯和甲基丙烯酸甲酯的质量比为1:1～1:5。
优选的，所述反应型乳化剂SR-10和十二烷基硫酸钠的质量比为10:1～10:4。
优选的，所述消泡剂选自矿物油类、有机硅类和聚醚类中的一种或多种。
优选的，所述防腐剂选自卡松和苯甲酸钠中的一种或多种。
优选的，所述pH调节剂选自碳酸氢钠，所述引发剂选自过硫酸钾。
本申请还提供了所述的水性丙烯酸乳液的制备方法，包括以下步骤：
a)按照配比，将甲基丙烯酸甲酯总量的95wt％、丙烯酸甲酯、甲基丙烯酸和N-氨基丙烯酰胺混合，再加入复配乳化剂总量的70wt％，得到第一混合液；将软水总量的20wt％和引发剂总量的60wt％混合，得到第二混合液；
b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂和pH调节剂混合，反应，得到反应液；
c)将第一混合液、第二混合液和反应液混合，反应；
d)将步骤c)得到的反应液与消泡剂混合后抽真空，再加入防腐剂、润湿剂和成膜剂，得到水性丙烯酸乳液。
优选的，步骤b)中，所述反应的温度为80～90℃，时间为0.5～1h，步骤c)中，所述反应的温度为80～90℃，时间为1～2h。
优选的，步骤d)中，抽真空前还包括降温至40～60℃。
本申请提供了一种水性丙烯酸乳液，其由以下原料制备得到：10wt％～50wt％的丙烯酸酯混合物；1wt％～10wt％的成膜剂，0.5wt％～2wt％的润湿剂，1wt％～3wt％的复配乳化剂，0.2wt％～0.5wt％的消泡剂，0.1wt％～0.3wt％的防腐剂，0.1wt％～0.3wt％的引发剂，0.1wt％～0.2wt％的pH调节剂，35wt％～87wt％的软水。本发明的水性丙烯酸乳液，在单体中特别添加了N-氨基丙烯酰胺参与聚合反应，使乳液分子链上带有氨基和酰胺基，氨基和酰胺基不仅同样可以在乳液成膜时进行交联形成三维网状结构，增强乳液的耐水性能和成膜硬度，而且分子链上的氨基还可以与醛基进行反应，使涂层具备吸收甲醛的能力；采用反应型乳化剂SR-10和十二烷基硫酸钠进行复配，可以有效促进对各组分的乳化和分散，提高各组分之间的相容性，有效减少出渣，进一步提高了乳液的耐水性能、阻隔性能及稳定性；成膜剂采用三乙二醇二异辛酸酯，其不仅本身的气味更小，且其加入丙烯酸乳液后可以完全进入聚合物粒子中，润湿剂为大分子聚醚改性聚酯，其不仅具有良好的防缩孔能力，乳液成膜时均匀平整，且成膜时还会与乳液分子链进行交联，进一步增强阻隔性能和耐水性能。因此，本申请通过加入上述组分并调节上述组分的含量，使得水性丙烯酸乳液具有高阻隔性和高耐水性。进一步的，本申请限定了丙烯酸甲酯和甲基丙烯酸甲酯的比例，使得乳液可以具有较高的Tg值，进一步提高成膜时的硬度，且乳液阻隔性能优秀。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
鉴于现有技术中水性丙烯酸乳液阻隔甲醛释放效果差且耐水性差的问题，本申请提供了一种高阻隔和高耐水的水性丙烯酸乳液，对甲醛具有良好阻隔性，可有效降低甲醛的释放量，同时乳液具有优秀的耐水性能；乳液本身为纯水性材料，环保无毒，无刺激性气味，且涂层透明、硬度大。具体的，本发明实施例公开了一种高阻隔和高耐水的水性丙烯酸乳液，由以下原料制备得到：
Figure PCTCN2021090134-appb-000003
Figure PCTCN2021090134-appb-000004
所述丙烯酸酯混合物中包括N-氨基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯和甲基丙烯酸；
所述复配乳化剂为反应型乳化剂SR-10和十二烷基硫酸钠；
所述成膜剂为三乙二醇二异辛酸酯；
所述润湿剂为大分子聚醚改性聚酯。
在本申请所述丙烯酸乳液中，所述丙烯酸酯混合物主要影响成膜厚度，在具体实施例中，所述丙烯酸甲酯和甲基丙烯酸甲酯的质量比为1:1～1:5；更具体的，所述丙烯酸甲酯和甲基丙烯酸甲酯的质量比1:1、1:2、1:3、1:4或1:5。上述丙烯酸酯混合物中N-氨基丙烯酰胺参与聚合反应，使乳液分子链上带有氨基和酰胺基，氨基和酰胺基不仅同样可以在乳液成膜时进行交联形成三维网状结构，增强乳液的耐水性能和成膜硬度，而且分子链上的氨基还可以与醛基进行反应，使涂层具备吸收甲醛的能力；特定比例的丙烯酸甲酯和甲基丙烯酸甲酯的，使得乳液可以具有较高的Tg值，进一步提高成膜时的硬度，且乳液阻隔性能优秀；甲基丙烯酸为水溶性单体，可以增强附着力，使成膜对基材的附着力显著提升。所述丙烯酸酯混合物中还包括甲基丙烯酸乙酯和丙烯酸乙酯；其调节聚合物的玻璃化转变温度，调整乳液的最低成膜温度和成膜硬度。所述丙烯酸酯混合物的含量为10～50wt％，更具体的，所述丙烯酸酯混合物的含量为20～40wt％。
所述复配乳化剂为反应型乳化剂烯丙基羟烷基磺酸钠(反应型乳化剂SR-10)和十二烷基硫酸钠，其质量比为10:1～10:4，更具体的，所述反应型乳化剂SR-10和十二烷基硫酸钠的质量比为10：1、10：2、10：3或10：4；两 者复配可以有效促进对各组分的乳化和分散，提高各组分之间的相容性，有效减少出渣，进一步提高了乳液的耐水性能、阻隔性能及稳定性。所述复配乳化剂的含量为1～3wt％，更具体的，所述复配乳化剂的含量为1wt％、2wt％或3wt％。
所述成膜剂选自三乙二醇二异辛酸酯，其不仅本身的气味更小，且其加入丙烯酸乳液后可以完全进入聚合物粒子中。所述成膜剂的含量为1～10wt％，更具体的，所述成膜剂的含量为2～9wt％。
所述润湿剂选自大分子聚醚改性聚酯，其不仅具有良好的防缩孔能力，乳液成膜时均匀平整，且成膜时还会与乳液分子链进行交联，进一步增强阻隔性能和耐水性能。所述润湿剂的含量为0.5wt％～2wt％，更具体的，所述润湿剂的含量为0.8～1.9wt％。
本申请复配乳化剂、成膜剂和润湿剂是保证水性丙烯酸乳液实现高阻隔、高耐水行的关键。
本申请中还包括助剂：消泡剂、防腐剂、引发剂、pH调节剂，其中，所述消泡剂选自矿物油类、有机硅类和聚醚类中的一种或多种，其含量为0.2～0.5wt％，更具体的，其含量为0.3wt％、0.4wt％、0.5wt％或0.2wt％；所述防腐剂选自卡松和苯甲酸钠中的一种或多种，其含量为0.1～0.3wt％，更具体的，其含量为0.1wt％、0.2wt％或0.3wt％；所述pH调节剂选自碳酸氢钠，其含量为0.1～0.2wt％；所述引发剂选自过硫酸钾，其含量为0.1～0.3wt％，更具体的，其含量为0.1wt％、0.2wt％或0.3wt％。
本申请还提供了所述水性丙烯酸乳液的制备方法，包括以下步骤：
a)按照配比，将甲基丙烯酸甲酯总量的95wt％、丙烯酸甲酯、甲基丙烯酸和N-氨基丙烯酰胺混合，再加入复配乳化剂总量的70wt％，得到第一混合液；将软水总量的20wt％和引发剂总量的60wt％混合，得到第二混合液；
b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂和pH调节剂混合，反应，得到反应液；
c)将第一混合液、第二混合液和反应液混合，反应；
d)将步骤c)得到的反应液与消泡剂混合后抽真空，再加入防腐剂、润湿剂和成膜剂，得到水性丙烯酸乳液。
在上述制备过程中，步骤a)是一个预乳化过程，即反应单体和反应性乳化剂充分混合。在所述丙烯酸酯混合液中还包括甲基丙烯酸乙酯和丙烯酸乙酯时，也同时在加入复配乳化剂之前加入。
步骤b)是一个种子反应阶段，即甲基丙烯酸甲酯聚合过程，原料混合后搅拌温度升至80～90℃，保温30min。
步骤c)是主要反应阶段，单体聚合生成高聚物；上述第一混合液、第二混合液滴加至反应液中，3～5h滴完，保温1～2h，保温时的温度为80～90℃。
上述反应之后则加入消泡剂，待温度降至40～60℃时抽真空，以去除乳液中残余单体，有效减少乳液中的单体参与，降低乳液气味，此阶段持续4～12h待温度降至40℃以下，加入防腐剂、润湿剂和成膜剂，即得到水性丙烯酸乳液。
本发明提供的水性丙烯酸乳液涂覆到人造三合板上，其涂层可以有效阻隔三合板80％以上的甲醛释放，有效降低甲醛释放量，使空气中的游离态甲醛分子含量明显降低；将三合板放入水中浸泡72小时涂层无发白、溶胀现象，且不影响阻隔性能，可广泛应用于外墙涂料、木制家具涂层上，应用时不影响使用性能或外观。同时，乳液的成膜硬度大，涂层透明高光泽，无刺激性气味。
为了进一步理解本发明，下面结合实施例对本发明提供的水性丙烯酸乳液及其制备方法进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例1
一种高阻隔和高耐水的水性丙烯酸乳液，由下述重量含量的原料配制成：丙烯酸酯混合物10％、成膜剂1％、润湿剂0.5％、复配乳化剂1％、消泡剂0.2％、防腐剂0.1％、引发剂0.1％、pH调节剂0.1％，软水87％；丙烯酸酯混合物由甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺混合而得，其中丙烯酸甲酯和甲基丙烯酸甲酯的混合比例为1:1；复配乳化剂为反应型乳化剂SR-10和十二烷基硫酸钠的复配，复配比例为10:1；成膜剂为三乙二醇二异辛酸酯；润湿剂为大分子聚醚改性聚酯；消泡剂为矿物油类；防腐剂为苯甲酸钠；pH调节剂为碳酸氢钠；引发剂为过硫酸钾。
一种高阻隔和高耐水的水性丙烯酸乳液制备方法，包括如下步骤：
a)先将甲基丙烯酸甲酯总量的95％以及甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺进行混合，再加入复配乳化剂总量的70％，搅拌30min后备用；用软水总量的20％将引发剂总量的60％溶解，备用；
b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂以及pH调节剂加入反应釜内，搅拌速度为300r/min，待温度升至85℃，保温30min；
c)将步骤(a)中已配置好的单体和引发剂溶液缓慢滴加入反应釜内，3h滴完，滴加时保持匀速；滴加完毕，保温1h，保温时温度为80℃；
d)加入消泡剂，维持搅拌速度为300r/min，待温度降至60℃时抽真空，去除乳液中的残余单体，持续4h；
e)待温度降至40℃以下，维持搅拌速度为300r/min，加入防腐剂、润湿剂和成膜剂，搅拌均匀后过滤出料，制得水性丙烯酸乳液。
实施例2
一种高阻隔和高耐水的水性丙烯酸乳液，由下述重量含量的原料配制成：丙烯酸酯混合物50％、成膜剂9％、润湿剂2％、复配乳化剂3％、消泡剂0.3％、防腐剂0.3％、引发剂0.3％、pH调节剂0.1％，软水35％；丙烯酸酯混合物由甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺混合而得，其中丙烯酸甲酯和甲基丙烯酸甲酯的混合比例为1:5；复配乳化剂为反应型乳化剂SR-10和十二烷基硫酸钠的复配，复配比例为10:4；成膜剂为三乙二醇二异辛酸酯；润湿剂为大分子聚醚改性聚酯；消泡剂为矿物油类和有机硅类的混合物；防腐剂为卡松；pH调节剂为碳酸氢钠；引发剂为过硫酸钾。
一种高阻隔和高耐水的水性丙烯酸乳液制备方法，包括如下步骤：
a)先将甲基丙烯酸甲酯总量的95％以及甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺进行混合，再加入复配乳化剂总量的70％，搅拌30min后备用；用软水总量的20％将引发剂总量的60％溶解，备用；
b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂以及pH调节剂加入反应釜内，搅拌速度为300r/min，待温度升至90℃，保温30min；
c)将步骤(a)中已配置好的单体和引发剂溶液缓慢滴加入反应釜内，5h滴完，滴加时保持匀速；滴加完毕，保温2h，保温时温度为90℃；
d)加入消泡剂，维持搅拌速度为300r/min，待温度降至40℃时进行抽真空，去除乳液中的残余单体，持续12h；
e)待温度降至40℃以下，维持搅拌速度为300r/min，加入防腐剂、润湿剂和成膜剂，搅拌均匀后过滤出料，制得水性丙烯酸乳液。
实施例3
一种高阻隔和高耐水的水性丙烯酸乳液，由下述重量含量的原料配制成：丙烯酸酯混合物40％、成膜剂10％、润湿剂1.9％、复配乳化剂2％、消泡剂0.5％、防腐剂0.2％、引发剂0.2％、pH调节剂0.2％，软水45％；丙烯酸酯混合物由甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺混合而得，其中丙烯酸甲酯和甲基丙烯酸甲酯的混合比例为1:3；复配乳化剂为反应型乳化剂SR-10和十二烷基硫酸钠的复配，复配比例为10:2；成膜剂为三乙二醇二异辛酸酯；润湿剂为大分子聚醚改性聚酯；消泡剂为聚醚类；防腐剂为卡松和苯甲酸钠的混合物；pH调节剂为碳酸氢钠；引发剂为过硫酸钾。
一种高阻隔和高耐水的水性丙烯酸乳液制备方法，包括如下步骤：
a)先将甲基丙烯酸甲酯总量的95％以及甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺进行混合，再加入复配乳化剂总量的70％，搅拌30min后备用；用软水总量的20％将引发剂总量的60％溶解，备用；
b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂，以及pH调节剂加入反应釜内，搅拌速度为300r/min，待温度升至87℃，保温30min；
c)将步骤(a)中已配置好的单体和引发剂溶液缓慢滴加入反应釜内，3.3h滴完，滴加时保持匀速；滴加完毕，保温1.6h，保温时温度为84℃；
d)加入消泡剂，维持搅拌速度为300r/min，待温度降至50℃时进行抽真空，去除乳液中的残余单体，持续7h；
e)待温度降至40℃以下，维持搅拌速度为300r/min，加入防腐剂、润湿剂和成膜剂，搅拌均匀后过滤出料，制得水性丙烯酸乳液。
对比例1
实施例1中的丙烯酸酯混合物由甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸、N-氨基丙烯酰胺混合而得，其中丙烯酸甲酯和甲基丙烯酸甲酯的混合比例为1:1，替换为：丙烯酸酯混合物由甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸混合而得，其中丙烯酸甲酯和甲基丙烯酸甲酯的混合比例为1:7，其余配方与制备方法不变。
对比例2
实施例2中的成膜剂为三乙二醇二异辛酸酯，润湿剂为大分子聚醚改性聚酯，替换为：成膜剂为二丙二醇甲醚，润湿剂为Glide 496，其余配方与制备方法不变。
将本发明实施例1～3和对比例1～2制得的水性丙烯酸乳液涂覆到人造三合板上，检测三合板7.5小时内的甲醛释放浓度，并将三合板放入水中浸泡时的耐水性能，检测结果如表1：(空白对照为未涂覆丙烯酸乳液的人造三合板)
表1实施例和对比例制备的水性丙烯酸乳液的性能数据表
Figure PCTCN2021090134-appb-000005
由表1可知，采用实施例1～3所制得的水性丙烯酸乳液涂覆的人造三合板，甲醛释放浓度低，丙烯酸乳液可有效阻隔甲醛释放；三合板泡水72小时均无发白现象，耐水性能好；乳液成膜透明高光泽，无刺激性气味。采用对比例1～2所制得的水性丙烯酸乳液涂覆的人造三合板，甲醛释放浓度较高，三合板泡水一段时间内均出现发白现象，且有刺激性气味。
本发明的水性丙烯酸乳液，在单体中特别添加了N-氨基丙烯酰胺参与聚合反应，使乳液分子链上带有氨基和酰胺基，氨基和酰胺基不仅同样可以在乳液成膜时进行交联形成三维网状结构，增强乳液的耐水性能和成膜硬度，而且分子链上的氨基还可以与醛基进行反应，使涂层具备吸收甲醛的能力；通过限定丙烯酸甲酯和甲基丙烯酸甲酯的混合比例，乳液可以具有较高的Tg值，进一步提高成膜时的硬度，且乳液阻隔性能优秀；采用反应型乳化剂SR-10和十二烷基硫酸钠进行复配使用，可以有效促进对各组分的乳化和分散，提高各组分之间的相容性，有效减少出渣，进一步提高了乳液的耐水性能、阻隔性能及稳定性，相比于使用单一乳化剂的丙烯酸乳液，本发明的保质期可由原来的4个月延长为12个月。本发明配方中的所有助剂均不会产生较大的刺激性气味，再加上生产过程中会通过抽真空的方式，彻底去除乳液中的残余单体，使得可以制备得到无刺激性气味的丙烯酸乳液。
市场上常用的醇酯、二醇醚类成膜剂，由于具有水溶性，加入丙烯酸乳液后部分会介于水相与高聚物相之间，因此需要较多的添加量才能较好的促进乳液的成膜，且添加后还会影响乳液的耐水性能。本发明的成膜剂采用三乙二醇二异辛酸酯，不仅本身的气味更小，且其加入丙烯酸乳液后可以完全进入聚合物粒子中，故在较低添加比例时就可以有效降低乳液的最低成膜温度，促进乳液成膜，且不会影响乳液本身的耐水性能。同时，市场上常用的聚醚硅氧烷共聚物以及炔二醇类润湿剂，添加后会使丙烯酸乳液的耐水性能降低，而本发明使用的润湿剂为大分子聚醚改性聚酯，其不仅具有良好的防缩孔能力，乳液成膜时均匀平整，且成膜时还会与乳液分子链进行交联，进一步增强阻隔性能和耐水性能。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还 可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种高阻隔和高耐水的水性丙烯酸乳液，由以下原料制备得到：
    Figure PCTCN2021090134-appb-100001
    所述丙烯酸酯混合物中包括N-氨基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯和甲基丙烯酸；
    所述复配乳化剂为反应型乳化剂烯丙基羟烷基磺酸钠和十二烷基硫酸钠；
    所述成膜剂为三乙二醇二异辛酸酯；
    所述润湿剂为大分子聚醚改性聚酯。
  2. 根据权利要求1所述的水性丙烯酸乳液，其特征在于，所述丙烯酸酯混合物中还包括甲基丙烯酸乙酯和丙烯酸乙酯。
  3. 根据权利要求1或2所述的水性丙烯酸乳液，其特征在于，所述丙烯酸酯混合物中，所述丙烯酸甲酯和甲基丙烯酸甲酯的质量比为1:1～1:5。
  4. 根据权利要求1或2所述的水性丙烯酸乳液，其特征在于，所述反应型乳化剂SR-10和十二烷基硫酸钠的质量比为10:1～10:4。
  5. 根据权利要求1所述的水性丙烯酸乳液，其特征在于，所述消泡剂选自矿物油类、有机硅类和聚醚类中的一种或多种。
  6. 根据权利要求1所述的水性丙烯酸乳液，其特征在于，所述防腐剂选自卡松和苯甲酸钠中的一种或多种。
  7. 根据权利要求1所述的水性丙烯酸乳液，其特征在于，所述pH调节剂选自碳酸氢钠，所述引发剂选自过硫酸钾。
  8. 权利要求1所述的水性丙烯酸乳液的制备方法，包括以下步骤：
    a)按照配比，将甲基丙烯酸甲酯总量的95wt％、丙烯酸甲酯、甲基丙烯酸和N-氨基丙烯酰胺混合，再加入复配乳化剂总量的70wt％，得到第一混合液；将软水总量的20wt％和引发剂总量的60wt％混合，得到第二混合液；
    b)将剩余的软水、甲基丙烯酸甲酯、复配乳化剂、引发剂和pH调节剂混合，反应，得到反应液；
    c)将第一混合液、第二混合液和反应液混合，反应；
    d)将步骤c)得到的反应液与消泡剂混合后抽真空，再加入防腐剂、润湿剂和成膜剂，得到水性丙烯酸乳液。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤b)中，所述反应的温度为80～90℃，时间为0.5～1h，步骤c)中，所述反应的温度为80～90℃，时间为1～2h。
  10. 根据权利要求9所述的制备方法，其特征在于，步骤d)中，抽真空前还包括降温至40～60℃。
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