WO2020248452A1 - Dispersion aqueuse de polyacrylate d'hydroxyle contenant du fluor à forte teneur en extrait sec, son procédé de préparation et son utilisation - Google Patents

Dispersion aqueuse de polyacrylate d'hydroxyle contenant du fluor à forte teneur en extrait sec, son procédé de préparation et son utilisation Download PDF

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WO2020248452A1
WO2020248452A1 PCT/CN2019/111354 CN2019111354W WO2020248452A1 WO 2020248452 A1 WO2020248452 A1 WO 2020248452A1 CN 2019111354 W CN2019111354 W CN 2019111354W WO 2020248452 A1 WO2020248452 A1 WO 2020248452A1
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fluorine
water
solid content
monomer
polyacrylate
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PCT/CN2019/111354
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Chinese (zh)
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瞿金清
刘栋
朱延安
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华南理工大学
嘉宝莉化工集团股份有限公司
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Publication of WO2020248452A1 publication Critical patent/WO2020248452A1/fr

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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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D5/16—Antifouling paints; Underwater paints

Definitions

  • the invention relates to a hydroxy polyacrylate water dispersion, in particular to a high solid content fluorine-containing hydroxy polyacrylate water dispersion with high solid content, low viscosity, good hydrophilicity and good compatibility with curing agents
  • the preparation method and application thereof belong to the field of fine chemical synthesis.
  • Two-component waterborne polyurethane coatings have high performance and low VOC content, and are one of the most concerned varieties in the coating field in recent years.
  • 2K-WPU contains a polyisocyanate component and a hydroxyl component.
  • water-based hydroxy acrylic resin is a common hydroxy component, which has the characteristics of good gloss, strong adhesion, and good film formation, but it also has the disadvantages of hot stickiness and cold brittleness and poor water resistance to the coating film.
  • the water-based hydroxy acrylic resin can be hydroxy acrylic emulsion and hydroxy acrylic water dispersion.
  • the hydroxy acrylic water dispersion has the characteristics of controllable molecular weight, uniform distribution, good dispersibility, and better storage stability, and it does not contain free emulsifiers. It can prepare acrylic resins with higher hydroxyl content, which is beneficial to the curing agent. The reaction increases the crosslinking density and improves the performance of the coating film.
  • the existing hydroxy acrylic water dispersion products mainly have low solid content and poor waterproof and anti-fouling performance on the surface of the coating film, which affects the promotion and application of 2K-WPU coatings.
  • the commonly used method is to increase the content of hydrophilic groups and increase the hydrophilicity of the water dispersion to increase the solid content.
  • hydrophilic monomers there is a problem of excessive amount of hydrophilic monomers.
  • the Chinese invention patent CN201810886099.8 application discloses a method for preparing a high-performance water-soluble high-solid low-viscosity acrylic resin. This method prepares a water-soluble acrylic resin with high solid content and low viscosity, and the amount of hydrophilic acrylic acid is as high as 7 ⁇ 12%, affecting the water resistance and hydrophobicity of the coating film.
  • the addition of functional vinyl macrocyclic monomers can significantly reduce the viscosity, but there is an excessive amount of macrocyclic monomers, which reduces the conversion rate of the monomers and increases the manufacturing cost.
  • the Chinese invention patent CN201610019259.X application discloses a high-solid high-gloss fast Dry water-soluble hydroxy acrylic resin and its preparation method. The method prepares a water-soluble acrylic resin with high solid content and low viscosity by adding vinyl macrocyclic monomer, and the amount of vinyl macrocyclic monomer is as high as 20-50%. Affect the flexibility of the coating film and increase the product cost.
  • fluorine-containing monomers are generally selected for modification.
  • Two forms can be used, one is physical blending, and the other is chemical grafting of fluorine-containing vinyl monomers into acrylic resins.
  • Chinese invention patent 201310560679.5 discloses a water-soluble fluorosilicon-modified acrylate polymer and its preparation method and use.
  • the water-soluble fluorosilicon-modified acrylate polymer is composed of the following components by weight percentage: methyl methacrylate 20-50%, butyl acrylate 15-40%, acrylic acid 5-15%, hydroxyethyl methacrylate 5-15%, fluorinated acrylic monomer 10-35%, vinyl silicone prepolymer 1-3 % And initiator 1%; after the monomers are uniformly mixed during preparation, they are prepared by free radical polymerization and neutralized to form a salt.
  • the coating film prepared by this technology has good aging resistance, but its fluorine-containing acrylic monomer is as high as 10-35%, which severely reduces the hardness of the coating film and at the same time reduces the recoatability of the coating film.
  • the primary purpose of the present invention is to provide a high solid content, low viscosity, good stability, good compatibility with the curing agent, and environment-friendly high solid content fluorinated hydroxy polyacrylate aqueous dispersion and The method of preparation.
  • Another object of the present invention is to provide the application of high solid content fluorine-containing hydroxyl polyacrylate water dispersion in two-component polyurethane coatings; the prepared two-component polyurethane coating film has high gloss, good flexibility and adhesion Good, high hardness, good waterproof and stain resistance, good wear resistance.
  • a high solid content fluorine-containing hydroxy polyacrylate water dispersion its mass percentage composition is: fluorine-containing hydroxy polyacrylate solid resin is 44-51%, organic solvent is 5-15%, and the remainder is water;
  • the raw material composition of the fluorine-containing hydroxyl polyacrylate solid resin is: 33 to 38% of alkyl methacrylate, 3 to 7% of alkyl acrylate, and 15 to 25% of hydroxy acrylic monomer.
  • the high steric hindrance vinyl monomer is one or more of methyl styrene, benzyl methacrylate, vinyl tertiary carbonate, cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate Species
  • the vinyl sulfonate monomer is 2-acrylamido-2-methylpropanesulfonic acid, sodium vinylsulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, and allyloxy
  • the fluorine-containing vinyl monomer is trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate
  • the solid content of the fluorine-containing hydroxyl polyacrylate aqueous dispersion is 44-51wt%, the hydroxyl content is 1-6%, the viscosity at 25°C is 200-1000mP ⁇ s, the particle size is 40-120nm; the appearance is milky white Or light yellow semi-permeable liquid.
  • the alkyl methacrylate is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate and pentyl methacrylate .
  • the alkyl acrylate is one or more of methyl acrylate, ethyl acrylate, butyl acrylate and isooctyl acrylate.
  • the hydroxy acrylic monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
  • the neutralizer is triethylamine, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methylmorphine and 2 -One or more mixtures of amino-2-methylpropanol, the addition amount of which is 1.4% to 1.7% of the polyacrylate solid resin.
  • the organic solvent is one of N,N-dimethylformamide, isopropanol, diacetone alcohol, propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether and acetone.
  • the initiator is an azo initiator, which can be azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl azobisisobutyrate (V601 , AIBME), azobisisobutamidine hydrochloride (AIBA) and azobisisobuimidazoline hydrochloride (AIBI) or a mixture of more than two.
  • AIBN azobisisobutyronitrile
  • ABSVN azobisisoheptonitrile
  • V601 , AIBME dimethyl azobisisobutyrate
  • AIBA azobisisobutamidine hydrochloride
  • AIBI
  • the chain transfer agent is one or more mixtures of mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, dodecyl mercaptan and ⁇ -methylstyrene dimer.
  • the preparation method of the high solid content fluorine-containing hydroxyl polyacrylate water dispersion under the protection of nitrogen, the fluorine-containing vinyl monomer, vinyl sulfonate monomer, alkyl methacrylate, alkyl acrylate Ester, hydroxy acrylic monomer, high hindrance vinyl monomer, acrylic acid, initiator, chain transfer agent and organic solvent are mixed to prepare a mixed liquid.
  • the stirring speed is 500-1500 rpm; the rotating speed of the disperser for emulsification with water is 500-3000 rpm.
  • the high solid content fluorine-containing hydroxyl polyacrylate water dispersion is mixed with the defoamer and wetting agent, and dispersed for 10-20 minutes to obtain the water-based hydroxyl component; wherein the mass percentage of the water-based hydroxyl resin is composed of: high solids
  • the content is 70-85% fluorine-containing hydroxy polyacrylate water dispersion, defoamer 0.05-0.3%, wetting/0.1-0.25%, others are water; when using, mix the water-based hydroxyl component with the water-based polyisocyanate curing agent , Control the molar ratio of NOC/OH in the mixture to 0.5 ⁇ 3:1, mechanically stir for 5 ⁇ 10min to obtain a two-component polyurethane coating;
  • the defoaming agent is TEGO-805, TEGO-810, TEGO-815, TEGO-825 and BYK's modified polysiloxane copolymer solution BYK- 011.
  • the wetting agent is one or more of BYK's polyether modified polysiloxane solution BYK-349, BYK-378, TEGO's TEGO-245, and TEGO-450.
  • the water-based polyisocyanate curing agent is one or more of the hydrophilic modified hexamethylene diisocyanate Bayhydur 3100, Bayhydur XP 2655, Bayhydur XP 2759, Bayhydur XP 2487 and the like of Bayer Company.
  • the coating film obtained by the invention has the characteristics of strong hydrophobicity, high hardness, good adhesion, good flexibility, good stain resistance, and excellent solvent resistance, and can be widely used in various wood furniture, industrial anticorrosion and other fields.
  • the present invention has the following advantages and beneficial effects:
  • the present invention uses vinyl sulfonate to synergize with a small amount of vinyl functional monomers with huge steric hindrance branched structure to prepare an aqueous hydroxy polyacrylate dispersion with a solid content of up to 51%.
  • the method not only significantly reduces the viscosity of the water dispersion, and prepares a higher solid content acrylic water dispersion; but also can increase the rigidity of the polymer and increase the hardness of the coating film.
  • the present invention uses a fluorine-containing vinyl monomer to chemically graft the polyacrylic acid polyester water dispersion to give the water-based two-component coating film more durable stain resistance, abrasion resistance and other physical and mechanical properties; and A very small amount of fluorine-containing vinyl monomer can achieve good waterproof and anti-staining effects.
  • the water-based paint prepared by the invention is stable in storage, low in VOC, and has the advantages of green and environmental protection.
  • Figure 1 is the infrared spectrum of the high solid content fluorine-containing hydroxy polyacrylate aqueous dispersion of Example 1.
  • Figure 2a shows the morphology of the stain droplets on the fluorine modified coating film in Example 1;
  • Figure 2b shows the morphology of the stain droplets on the unmodified coating film in Example 1;
  • Figure 2c is a diagram showing the morphology of the stain droplets in Example 1 after being placed on the fluorine-modified coating film for 24 hours;
  • Figure 2d is a droplet morphology diagram of the stain droplets in Example 1 after being placed on the unmodified coating film for 24 hours;
  • Fig. 3 is a diagram showing the sliding morphology of 10wt% NaCl droplets on the unmodified coating film and on the fluorine-modified coating film in Example 1.
  • the coating film is set on a wooden board inclined at 45°.
  • the percentages (%) are all mass percentages.
  • the performance of vinyl fluoromonomer modified polyacrylate water dispersion and two-component waterborne coatings is tested by the following method: According to ASTMD2196-1986, the water dispersion of vinyl fluoromonomer modified polyacrylate water is measured by Brookfied RVF rotary viscometer.
  • the viscosity of the body; the solid content of the vinyl fluorine monomer modified polyacrylate aqueous dispersion is measured according to GB1725-79; the hardness of the coating film is tested according to GB/6379-2006; the adhesion of the coating film is measured according to the Chinese version of ISO2409-2007; GB/T 9754-2007 determines the gloss of the coating film; determines the tea resistance of the coating film according to GB 23999-2009; determines the water absorption of the coating film according to GB/T 23999-2009; determines the salt resistance of the coating film according to GB/T-1763-1979 Performance; according to GB/1731-93 to measure the flexibility of the coating film; according to GB/T 9780-2013 to measure the stain resistance of the coating film.
  • the vinyl fluoride monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent are mixed to prepare a mixed solution, and 10% of the mixed solution is added to the reactor.
  • High-speed dispersion was performed at 30°C and 1000 rpm to prepare an aqueous dispersion.
  • High solid content fluorinated hydroxy polyacrylate water dispersion properties solid content is 45%, viscosity (25°C) is 900mPa ⁇ s, hydroxyl content is 4%, average particle size is 80nm, volatile organic content is 90g/L, Appearance is light yellow semi-permeable liquid.
  • the absorption peaks at 1165 cm -1 and 1244 cm -1 are the tensile vibration absorption peaks of the CF 2 group and the CF 3 group, respectively, which proves that the vinyl fluoride monomer participates in the copolymerization reaction.
  • the broadening of the nearby peak shape is due to the coincidence with the deformation vibration absorption peak of the hydroxyl group.
  • Infrared spectroscopy has synthesized an aqueous dispersion of hydroxy polyacrylate.
  • Figures 2a-2d are the droplet morphology diagrams of various stain droplets on the coating film. The stain resistance is judged by the droplet morphology. From left to right, the droplets are rapeseed oil, olive oil, peanut oil, black tea, tap water, 10% NaCl, 10% NaOH, and 5% H 2 SO 4 .
  • Figure 2a is a droplet morphology diagram of stain droplets on a fluoromonomer modified coating film
  • Figure 2b is a droplet morphology diagram of the stain droplets on an unmodified coating film
  • Figure 2c is a stain droplet shape diagram that contains The morphology of the droplets after being placed on the modified fluoromonomer coating film for 24 hours.
  • Figure 2d is the morphology of the droplets after being placed on the unmodified coating film for 24 hours. From the comparison of Figure 2a and Figure 2b, it can be seen that when a very small amount of fluorine-containing monomer is added, the contact angle of stain droplets on the surface of the fluorine-containing coating film is larger than that of the unmodified coating film, and the contact angle of water reaches 90° The above shows that the fluorine-containing coating film can produce better repellency to all kinds of stains, that is, better stain resistance.
  • Figure 3 is a diagram of the sliding morphology of 10wt% NaCl droplets on the unmodified coating film and on the fluorine-modified coating film in Example 1.
  • the coating film is set on a wooden board inclined at 45° and judged by the morphology. Stain resistance.
  • the graph e shows the sliding condition of 10wt% NaCl droplets on the unmodified coating film
  • the graph f shows the sliding resistance condition of the 10wt% NaCl droplets on the fluorine modified coating film of Example 1. From the comparison of e and f in Fig. 3, it can be seen that, compared with the unmodified coating film, 10wt% NaCl droplets slide on the fluorine-modified coating film as droplets without leaving any traces, and the stain resistance is better.
  • Table 2 and Figures 1 to 3 illustrate that the present invention uses the vinyl sulfonate monomer 2-acrylamido-2-methylpropanesulfonic acid and the large hindered monomer isobornyl methacrylate to prepare high solids content.
  • the aqueous hydroxy polyacrylic acid dispersion overcomes the shortcomings of the high viscosity of the hydroxy acrylic acid dispersion with high content of acrylic monomer as the hydrophilic monomer, and has the advantages of high solids and low viscosity.
  • Chinese invention patent CN201810886099.8 has a hydrophilic acrylic acid content as high as 7-12%, which affects the water resistance and hydrophobicity of the coating film.
  • Chinese invention patent application CN201610019259.X The amount of vinyl macrocyclic monomer is as high as 20-50%, which affects the flexibility of the coating film and increases the product cost;
  • Chinese invention patent 201310560679.5 fluorine-containing acrylic monomer is as high as 10-35%, which seriously reduces the coating film Hardness, while reducing the recoatability of the coating film.
  • acrylic acid 0.5-1.5%) is reduced by more than 4 times
  • vinyl macrocyclic monomer 8-15%) is reduced by more than 2 times
  • fluorine-containing acrylic monomer 0.04-1.0%) is reduced by more than 10 times.
  • the hydroxy polyacrylate aqueous dispersion prepared by the present invention does not introduce hydrophilic carboxyl groups and carboxylates through acrylic acid, but introduces vinyl sulfonates, which are more hydrophilic than carboxylates.
  • the amount of sulfonate added is much less than that of carboxylate, which can overcome the shortcomings of introducing a large amount of carboxylate to reduce the water resistance of the coating; on the other hand, vinyl sulfonate It is also a large sterically hindered vinyl monomer, combined with other large sterically hindered vinyl monomers, greatly reduces the viscosity of the hydroxy polyacrylate water dispersion, and the two have a synergistic effect to make the hydroxy polyacrylate water dispersion When the effect of high solids and low viscosity is achieved, the amount of vinyl hindered monomers is reduced by more than 2 times, which not only increases the solid content and film hardness of the water-based hydroxy resin, but also greatly reduces the cost of the water-based hydroxy resin.
  • fluorine-containing acrylic monomers will migrate to the film-air interface when the water-based paint is formed into a film, reducing the surface tension of the film, thereby improving the stain resistance of the film; when the amount of addition is higher
  • fluorine-containing segments are uniformly dispersed in the coating film, although it also improves the stain resistance and aging resistance of the coating film, a large number of fluorine-containing segments are distributed on the surface of the coating film, reducing the recoatability of the coating film and increasing Big paint cost.
  • the present invention finds that when the fluorine-containing monomer is added in an amount of 0.04-1.0%, the stain resistance of the coating film is enhanced without affecting the recoatability of the coating film.
  • the fluorine-containing monomer When the fluorine-containing monomer is added in an amount greater than 1%, the coating The stain resistance of the film is not significantly improved, and the recoatability of the coating film is also reduced. Therefore, the addition amount of the fluorine-containing acrylic monomer of the present invention is only 10% of the comparison technology, and the stain resistance effect of the comparison technology can also be achieved.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, the vinyl fluoride monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent are mixed to prepare a mixed solution. Add 10% of the mixed solution to the reactor, stir and raise the temperature to 75° C. to react for 30 minutes, add the remaining mixture to the reactor within 4 hours and keep the temperature for 1.5 hours to obtain a fluorohydroxy polyacrylate prepolymer. Then, the temperature is lowered to below 50°C, a neutralizing agent is added for neutralization, and water is added for high-speed dispersion at 30°C at 1500 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 46%, viscosity (25°C) is 600mPa ⁇ s, hydroxyl content is 4%, average particle size is 75nm, volatile organic content is 85g/L, Appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 15% of the mixed solution to the reactor, stir and raise the temperature to 75°C to react for 35min, add the remaining mixture to the reactor within 5h, and keep it for 1.5h to obtain the vinyl fluoride monomer modified Polyacrylate prepolymer. Then the temperature is lowered to below 50°C, a neutralizer is added for neutralization, and water is added for high-speed dispersion at 30°C at 2500 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 45%, viscosity (25°C) is 850mPa ⁇ s, hydroxyl content is 4%, average particle size is 90nm, volatile organic content is 100g/L, Appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 10% of the mixed solution to the reactor, stir and raise the temperature to 80°C for 30 minutes, add the remaining mixture to the reactor within 4.5, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then, the temperature is lowered to below 50°C, a neutralizing agent is added for neutralization, and water is added to perform high-speed dispersion at 30°C at 2000 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 44%, viscosity (25°C) is 650mPa ⁇ s, hydroxyl content is 4%, average particle size is 70nm, volatile organic gas content is 95g/L Appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 10% of the mixed solution to the reactor, stir and raise the temperature to 75°C to react for 30 minutes, add the remaining mixture to the reactor within 5, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then, the temperature is lowered to below 50°C, a neutralizing agent is added for neutralization, and water is added for high-speed dispersion at 30°C at 1500 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 48%, viscosity (25°C) is 662mPa ⁇ s, hydroxyl content is 4%, average particle size is 66nm, volatile organic gas content is 95g/L , The appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 10% of the mixed solution to the reactor, stir and raise the temperature to 75°C for 30 minutes, add the remaining mixture to the reactor within 4.5, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then the temperature is lowered to below 50°C, a neutralizer is added for neutralization, and water is added for high-speed dispersion at 30°C at 2500 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 48%, viscosity (25°C) is 780mPa ⁇ s, hydroxyl content is 4%, average particle size is 90nm, volatile organic content is 105g/L, Appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 20% of the mixed solution to the reactor, stir and raise the temperature to 75°C to react for 40 minutes, add the remaining mixture to the reactor within 4, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then the temperature is lowered to below 50°C, a neutralizer is added for neutralization, and water is added for high-speed dispersion at 30°C at 2500 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 48%, viscosity (25°C) is 523mPa ⁇ s, hydroxyl content is 3%, average particle size is 99nm, volatile organic content is 110g/L, Appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, combine vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 15% of the mixed solution to the reactor, stir and raise the temperature to 90°C to react for 35 minutes, add the remaining mixture to the reactor within 4, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then, the temperature is lowered to below 50°C, a neutralizing agent is added for neutralization, and water is added for high-speed dispersion at 30°C at 3000 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 50%, viscosity (25°C) is 580mPa ⁇ s, hydroxyl content is 5%, average particle size is 89nm, volatile organic gas content is 80g/L , The appearance is light yellow semi-permeable liquid.
  • Preparation of vinyl fluorine monomer modified polyacrylate under the protection of nitrogen, the vinyl fluoride monomer, vinyl silicon monomer, vinyl sulfonate monomer, acrylic monomer, initiator and chain transfer agent Mix and prepare a mixed solution, add 10% of the mixed solution to the reactor, stir and raise the temperature to 82°C to react for 30 minutes, add the remaining mixture to the reactor within 4, keep it for 2 hours, and obtain a vinyl fluoride monomer modified poly Acrylic prepolymer. Then, the temperature is lowered to below 50°C, a neutralizing agent is added for neutralization, and water is added to perform high-speed dispersion at 30°C at 2000 rpm to prepare an aqueous dispersion.
  • Vinyl fluorine monomer modified polyacrylate water dispersion properties solid content is 51%, viscosity (25°C) is 553mPa ⁇ s, hydroxyl content is 4%, average particle size is 55nm, volatile organic gas content is 93g/L , The appearance is light yellow semi-permeable liquid.
  • Examples 2-9 show different acrylic monomers, vinyl fluorine monomers, vinyl macrocyclic monomers, initiators, chain transfer agents and vinyl fluorine monomer modified polyolefins with different properties prepared by different processes.
  • Aqueous acid polyester dispersion It can be seen from the above examples that the water dispersion of hydroxy acrylic polyester modified with fluorine-containing vinyl monomer has high solid content, low viscosity, small particle size, and low VOC content, and is compounded with isocyanate curing agent.
  • the coating film has high hardness, good tea salt resistance and flexibility, good stain resistance, and excellent overall performance. It is suitable for two-component polyurethane coatings and industrial anticorrosive coatings used in various woodware.

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Abstract

L'invention concerne une dispersion aqueuse de polyacrylate d'hydroxyle contenant du fluor à forte teneur en extrait sec, son procédé de préparation et son utilisation. Le procédé de préparation implique : sous atmosphère d'azote, le mélange d'un monomère de vinyle contenant du fluor, d'un monomère de sulfonate de vinyle, d'un monomère acrylique, d'un initiateur et d'un agent de transfert de chaîne pour préparer une solution mixte, en ajoutant d'abord de 5 à 15 % de la solution mixte à un réacteur, l'agitation et le chauffage de celle-ci à 70 à 85 °C pour une réaction pendant 30 à 45 minutes, l'ajout du mélange restant au réacteur pendant 4 à 5,5 heures, et le maintien de la température pendant 1 à 2 heures pour obtenir un prépolymère de polyacrylate d'hydroxyle contenant du fluor ; puis son refroidissement à 50 °C ou moins, en ajoutant un neutralisant pour la neutralisation, et en ajoutant de l'eau pour l'émulsification pour obtenir le produit. La dispersion aqueuse de polyacrylate d'hydroxyle contenant du fluor préparée présente les avantages d'une forte teneur en extrait sec, d'une faible viscosité, d'une bonne hydrophilie et d'une bonne compatibilité avec un agent de durcissement. Un film de revêtement de polyuréthane à deux composants aqueux préparé présente les caractéristiques d'une forte hydrophobicité, d'une dureté élevée, d'une bonne adhérence, d'une bonne flexibilité, d'une bonne résistance aux taches et d'une excellente résistance aux solvants.
PCT/CN2019/111354 2019-06-13 2019-10-16 Dispersion aqueuse de polyacrylate d'hydroxyle contenant du fluor à forte teneur en extrait sec, son procédé de préparation et son utilisation WO2020248452A1 (fr)

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CN110256625B (zh) * 2019-06-13 2020-09-25 华南理工大学 高固体含量含氟羟基聚丙烯酸酯水分散体及其制备方法与应用
CN112175503B (zh) * 2020-10-09 2021-11-09 赵玮 一种超顺滑涂料
CN113122119B (zh) * 2021-04-16 2022-06-17 商丘市博大化工有限公司 一种核壳结构的高硬度耐污汽车用水性双组份聚氨酯涂料的制造和使用方法
CN113717623B (zh) * 2021-08-17 2022-05-13 安徽哈船新材料科技有限公司 一种自发泡多功能水性吸潮涂料及其制备方法
CN114940724B (zh) * 2022-06-28 2024-06-28 扬州绿邦化工有限公司 一种改性羟基丙烯酸分散体及其制备方法
CN115838555B (zh) * 2022-10-19 2024-01-02 中昊北方涂料工业研究设计院有限公司 一种有机玻璃用改性聚甲基丙烯酸甲酯涂料及其制备和使用方法
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