WO2023206768A1 - Émulsion auto-séchante, résistante au brouillard salin, d'acrylate et procédé de préparation associé et application correspondante - Google Patents

Émulsion auto-séchante, résistante au brouillard salin, d'acrylate et procédé de préparation associé et application correspondante Download PDF

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Publication number
WO2023206768A1
WO2023206768A1 PCT/CN2022/101298 CN2022101298W WO2023206768A1 WO 2023206768 A1 WO2023206768 A1 WO 2023206768A1 CN 2022101298 W CN2022101298 W CN 2022101298W WO 2023206768 A1 WO2023206768 A1 WO 2023206768A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
add
initiator
temperature
resistant self
Prior art date
Application number
PCT/CN2022/101298
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English (en)
Chinese (zh)
Inventor
李秋琼
房迎春
段家喜
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上海保立佳化学技术有限公司
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Publication of WO2023206768A1 publication Critical patent/WO2023206768A1/fr

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Classifications

    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated 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
    • C09D5/08—Anti-corrosive paints

Definitions

  • the invention relates to a salt spray-resistant self-drying acrylic emulsion and its preparation method and application, and belongs to the technical field of coatings.
  • the purpose of this invention is to synthesize an emulsion that has excellent salt spray corrosion resistance to steel substrates by introducing special functional monomers and changing the process.
  • the core of the technology is to introduce polymerizable acrylic acid phosphate and polymerizable Urea-based monomer, through appropriate proportions and appropriate feeding processes, the emulsion prepared in the steel structure coating can improve the adhesion between the coating and the substrate, thereby greatly improving its salt spray and corrosion resistance.
  • the invention provides a salt spray-resistant self-drying acrylic emulsion.
  • Each component in the raw materials for preparation includes: 40-60 parts by weight of deionized water, 38-58 parts of raw material monomers, and polymerizable acrylic phosphate.
  • the raw material monomers include styrene, n-butyl acrylate, methyl methacrylate, ethyl acrylate, isooctyl methacrylate, isooctyl acrylate, acrylic acid, methacrylic acid, acrylamide, methyl Various types of acrylamide.
  • the polymerizable acrylic phosphate monomer includes PAM100 and/or PAM200.
  • the polymerizable urea-based monomer includes MEEU50W and/or WAM-II.
  • the emulsifier includes anionic emulsifier and/or nonionic emulsifier, wherein the anionic emulsifier includes fatty alcohol polyoxyethylene ether sulfate, alkyl sulfate and alkyl alcohol ether amber. Acid, the nonionic emulsifier includes fatty alcohol polyoxyethylene ethers.
  • the initiator is a persulfate compound, including one or more of ammonium persulfate and potassium persulfate.
  • the buffering agent includes one or more of sodium bicarbonate, ammonium bicarbonate, sodium dihydrogen phosphate, and ammonia water.
  • the oxidizing agent includes one or more of hydrogen peroxide and tert-butyl hydroperoxide.
  • the reducing agent includes one or more of sodium bisulfite, sodium formaldehyde sulfoxylate, ascorbic acid, and erythorbic acid.
  • the neutralizing agent includes one or more of ammonia, dimethylethanolamine, 2-amino-2-methyl-1-propanol, sodium hydroxide, and potassium hydroxide.
  • the invention also provides a method for preparing a salt spray-resistant self-drying acrylic emulsion, which specifically includes the following steps:
  • Preparation of pre-emulsion Add a certain amount of water and emulsifier into the pre-emulsification kettle, start stirring to 200-350r/min, stir for 15-20 minutes, then add some raw material monomers to completely dissolve, and then slowly Add the remaining raw material monomers, increase the rotation speed to 400-600 rpm, and stir and disperse at high speed for 30-60 minutes to prepare a pre-emulsion;
  • Preparation of the initial priming initiator aqueous solution Add a certain amount of deionized water to a container, and then add a certain amount of initiator as the initial priming initiator, and fully dissolve it for later use;
  • step S5 When the temperature of the reaction kettle is stabilized at 80-90°C, take 3-10% of the pre-emulsion prepared in step S1 and flow it directly into the reaction kettle. At the same time, add the initial primer initiator aqueous solution prepared in step S3 and observe the reaction. The color of the kettle changes to blue and the temperature rises significantly;
  • step S6 After waiting for the reaction in the kettle for 10-15 minutes and the temperature stabilizing at 80-90°C, continue to drip the remaining pre-emulsion and the dripping initiator solution prepared in step S2 at a constant speed. Control the temperature at 80-90°C and add dropwise. The stirring speed during the process is increased by 15 rpm every 30 minutes;
  • step S11 After the temperature drops to the above range, drop the oxidant aqueous solution and the reducing agent aqueous solution prepared in step S9 at the same time.
  • the dropping time is 30 minutes and the temperature is maintained at 55-75°C;
  • steps S4, S5 and S6 is 82-86°C.
  • the temperature of steps S10, S11 and S12 is 65-75°C.
  • the polymer emulsion prepared by the above steps has a solid content of 45-47%, a pH of 7-9, a viscosity of 1500-5000 mPa.s, a theoretical glass transition temperature of the polymer of 30°C-60°C, and a minimum composition of The film temperature is between 20-45°C.
  • the present invention also provides an application of the above-mentioned salt spray-resistant self-drying acrylic emulsion in the field of coatings.
  • the technical characteristics and core advantages of the present invention are: by adding polymerizable acrylic acid phosphate monomer and polymerizable urea monomer, not only can the synthesis process be more stable, but also the hydrophilic segment of the outer layer of the polymer particles can be introduced It contains more phosphate ester groups and urea-based monomers, so that after the polymer paint film dries, it can better adhere to the steel substrate, and further passivates the steel substrate, thereby improving the corrosion resistance of the steel.
  • the salt spray-resistant self-drying acrylic emulsion paint prepared by this invention has more obvious salt spray resistance and anti-corrosion properties.
  • a method for preparing a salt spray-resistant self-drying acrylic emulsion which specifically includes the following steps:
  • Preparation of pre-emulsion Accurately weigh 185g of deionized water and 7.2g of anionic emulsifier sodium lauryl sulfate, put them into the pre-emulsification bottle, turn on stirring to 210r/min, stir for 15 minutes; then weigh accurately in sequence 7.3g acrylamide and 6.8g acrylic acid. After continuing to stir for 15 minutes, add 258.6g styrene, 88.2g n-butyl acrylate, and 78.9g isooctyl acrylate in sequence, increase the rotation speed to 420r/min, and disperse at high speed for 30 minutes to prepare Pre-emulsion;
  • step S5 When the temperature of the reaction kettle is stable at 82-86°C, take 45g of the pre-emulsion prepared in step S1 and add it directly into the reaction kettle. At the same time, add the initial primer aqueous solution prepared in step S3 and observe the color change in the reaction kettle. It is blue and the temperature has increased significantly;
  • step S6 Wait for the reaction in the kettle for 10-15 minutes. After the temperature stabilizes at 82-86°C, continue to drip the remaining pre-emulsion and the dripping initiator solution prepared in step S2 at a constant speed. Control the temperature at 82-86°C and add dropwise. The stirring speed during the process is increased by 15r/min every 30 minutes;
  • step S11 After the temperature drops to the above range, drip the oxidant aqueous solution and the reducing agent aqueous solution prepared in step S9 at the same time.
  • the dripping time is 30 minutes and the temperature is maintained at 55-75°C;
  • a method for preparing a salt spray-resistant self-drying acrylic emulsion which specifically includes the following steps:
  • Preparation of pre-emulsion Accurately weigh 185g of deionized water and 8.1g of anionic emulsifier A102, put them into the pre-emulsification bottle, turn on stirring to 210r/min, and stir for 15 minutes; then accurately weigh 7.3g of acrylamide, 6.8g of acrylic acid, continue stirring for 15 minutes, add 258.6g of styrene, 88.2g of n-butyl acrylate, and 78.9g of isooctyl acrylate, increase the rotation speed to 420r/min, and disperse at high speed for 30 minutes to prepare a pre-emulsion;
  • step S5 When the temperature of the reaction kettle is stable at 82-86°C, take 45g of the pre-emulsion prepared in step S1 and add it directly into the reaction kettle. At the same time, add the initial primer aqueous solution prepared in step S3 and observe the color change in the reaction kettle. It is blue and the temperature has increased significantly;
  • step S6 Wait for the reaction in the kettle for 10-15 minutes. After the temperature stabilizes at 82-86°C, continue to drip the remaining pre-emulsion and the dripping initiator solution prepared in step S2 at a constant speed. Control the temperature at 82-86°C and add dropwise. The stirring speed during the process is increased by 15r/min every 30 minutes;
  • step S11 After the temperature drops to the above range, drop the oxidant aqueous solution and the reducing agent aqueous solution prepared in step S9 at the same time.
  • the dropping time is 30 minutes and the temperature is maintained at 55-75°C;
  • a method for preparing a salt spray-resistant self-drying acrylic emulsion which specifically includes the following steps:
  • Preparation of pre-emulsion Accurately weigh 185g of deionized water and 7.6g of anionic emulsifier FES32, put them into the pre-emulsification bottle, turn on stirring to 210r/min, and stir for 15 minutes; then accurately weigh 7.3g of acrylamide, 6.8g of acrylic acid, continue stirring for 15 minutes, add 258.6g of styrene, 88.2g of n-butyl acrylate, and 78.9g of isooctyl acrylate, increase the rotation speed to 420r/min, and disperse at high speed for 30 minutes to prepare a pre-emulsion;
  • Nonionic emulsifier S90 start stirring to 160 rpm, start heating and circulating cooling water, and heat to 82-86°C;
  • step S5 When the temperature of the reaction kettle is stable at 82-86°C, take 45g of the pre-emulsion prepared in step S1 and add it directly into the reaction kettle. At the same time, add the initial primer aqueous solution prepared in step S3 and observe the color change in the reaction kettle. It is blue and the temperature has increased significantly;
  • step S6 Wait for the reaction in the kettle for 10-15 minutes. After the temperature stabilizes at 82-86°C, continue to drip the remaining pre-emulsion and the dripping initiator solution prepared in step S2 at a constant speed. Control the temperature at 82-86°C and add dropwise. The stirring speed during the process is increased by 15r/min every 30 minutes;
  • step S11 After the temperature drops to the above range, drip the oxidant aqueous solution and the reducing agent aqueous solution prepared in step S9 at the same time.
  • the dripping time is 30 minutes and the temperature is maintained at 55-75°C;
  • a method for preparing a self-drying acrylic emulsion with ordinary salt spray resistance is the same as Comparative Example 1, except that step S7 is omitted.
  • Example 1 Example 2
  • Example 3 Comparative ratio Solid content 46.7% 46.4% 46.6% 46.4% viscosity 2892mPa.s 2570mPa.s 2769mPa.s 2570mPa.s PH 7.3 7.4 7.5 7.4 particle size 101nm 104nm 103nm 104nm
  • Step 1 Add materials 1, 2, 3 and 4 in sequence and stir evenly at low speed (200-300r/min);
  • Step 2 Add substances 5, 6 and 7 in sequence, stir evenly at medium speed (500-800r/min), then adjust to high speed (1000-1500r/min) and grind for 30 minutes until the fineness is ⁇ 30 ⁇ m;
  • Step 3 Add substances 8-15 sequentially, stir for 10 minutes, adjust the viscosity to 90 ⁇ 5KU, filter and discharge the material, and prepare the coating.
  • Base material polished carbon steel plate and tinplate
  • the paint film made from the emulsion prepared by introducing polymerizable acrylic phosphate monomer and polymerizable urea monomer is better than the emulsion paint film prepared without adding these two types of materials.
  • the water resistance, salt water resistance and salt spray resistance have been significantly improved, proving that this type of self-drying acrylic emulsion has excellent anti-corrosion properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une émulsion auto-séchante, résistante au brouillard salin, d'acrylate qui est préparée à partir des constituants suivants, en parties en poids : 40 à 60 parties d'eau désionisée, 38 à 58 parties de monomères de matière première, 0,001 à 0,15 partie d'un monomère polymérisable de phosphate acrylique, 0,05 à 0,1 partie d'un monomère polymérisable de type carbamido, 0,5 à 2 parties d'un émulsifiant, 0,1 à 0,6 partie d'un initiateur, 0,1 à 0,5 partie d'un agent tampon, 0,05 à 0,1 partie d'un oxydant, 0,05 à 0,1 partie d'un agent réducteur et 0,2 à 0,6 partie d'un agent neutralisant. La présente invention concerne également un procédé de préparation de l'émulsion auto-séchante, résistante au brouillard salin, d'acrylate et une application correspondante dans le domaine des revêtements. Un revêtement préparé selon la formule et le procédé peut améliorer efficacement la résistance au brouillard salin et la résistance à la corrosion de l'acier.
PCT/CN2022/101298 2022-04-28 2022-06-24 Émulsion auto-séchante, résistante au brouillard salin, d'acrylate et procédé de préparation associé et application correspondante WO2023206768A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210462494.X 2022-04-28
CN202210462494.XA CN114891142A (zh) 2022-04-28 2022-04-28 一种耐盐雾自干型丙烯酸酯乳液及其制备方法和应用

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CN115895319B (zh) * 2022-08-25 2024-06-04 环涂士涂料有限公司 一种生物基抗菌除醛乳胶漆组合物及制备方法和应用

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