CN116515071A - Hybrid polyurethane dispersoid and preparation method and application thereof - Google Patents

Hybrid polyurethane dispersoid and preparation method and application thereof Download PDF

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Publication number
CN116515071A
CN116515071A CN202211301174.2A CN202211301174A CN116515071A CN 116515071 A CN116515071 A CN 116515071A CN 202211301174 A CN202211301174 A CN 202211301174A CN 116515071 A CN116515071 A CN 116515071A
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percent
prepolymer
organic solvent
polyurethane dispersion
hybrid polyurethane
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王宝文
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Jiangsu Jinyibo Innovative Materials Co ltd
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Jiangsu Jinyibo Innovative Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09D175/06—Polyurethanes from polyesters

Abstract

The invention relates to the technical field of paint, and relates to a hybrid polyurethane dispersoid and a preparation method and application thereof. Comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 15 to 22 percent of polyisocyanate, 3 to 5 percent of hydrophilic chain extender, 20 to 45 percent of polyester prepolymer, 0.2 to 0.5 percent of small molecule chain extender, 8 to 30 percent of acrylic acid prepolymer, 15 to 20 percent of organic solvent A, 5 to 8 percent of organic solvent B, 0.05 to 1 percent of catalyst and 2 to 5 percent of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 40-65% of polyalcohol and 40-65% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 20 to 65 percent of acrylic ester monomer, 0 to 15 percent of vinyl monomer, 20 to 50 percent of hydroxy acrylic ester monomer, 10 to 15 percent of organic solvent C and 0.5 to 3 percent of initiator.

Description

Hybrid polyurethane dispersoid and preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, in particular to the field of IPC C09D175, and further relates to a hybrid polyurethane dispersion, a preparation method and application thereof.
Background
The coiled material paint is used as a paint product for pre-coating metal sheets, changes the traditional mode of coating after metal sheet forming processing, but is used for pre-coating coiled material paint on the metal sheets to form color coated steel plates and then processing, and has more application in the fields of construction, household appliances, containers, automobile manufacturing, packaging containers, cooking utensils and the like. After the user purchases the precoated coiled material product, the precoated coiled material product can be directly processed into products with various shapes, and the products do not need to be recoated, so that the production process of the sheet metal product is greatly simplified, the paint loss during coating is reduced, and the harm to the environment and human body is reduced.
The existing precoated coiled material has high requirements on appearance, impact resistance and paint film flexibility of 0-1T, and needs better acid and alkali resistance, chemical resistance and corrosion resistance. Chinese patent CN201710699373.6 discloses a double-curing solvent-free polyurethane coiled material coating and a preparation method thereof, wherein the coating product comprises components of a double-glyceryl dendrimer polyurethane prepolymer, a castor oil-based polyurethane prepolymer, a composite active monomer, an inorganic composite filler, acetyl tributyl citrate, an ultraviolet curing agent, 3-10% of an aliphatic polyisocyanate curing agent, hydroxyethyl methacrylate phosphate and an epoxy silane coupling agent, and has good adhesive force, MEK wiping resistance, high and low temperature resistance and the like; but the curing time is long, and the acid and alkali resistance is required to be improved. Chinese patent CN 102827325A discloses a preparation of core-shell polyurethane/acrylic acid composite emulsion, the obtained composite emulsion is combined with crosslinking component, and is suitable for producing low VOC water-based coil coating; the preparation method is used for preparing the water-based coiled material coating finish paint film, and the hardness, the paint film flexibility and the MEK wiping resistance of the paint film are all to be improved.
Disclosure of Invention
In a first aspect, the present invention provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 15 to 22 percent of polyisocyanate, 3 to 5 percent of hydrophilic chain extender, 20 to 45 percent of polyester prepolymer, 0.2 to 0.5 percent of small molecule chain extender, 8 to 30 percent of acrylic acid prepolymer, 15 to 20 percent of organic solvent A, 5 to 8 percent of organic solvent B, 0.05 to 1 percent of catalyst and 2 to 5 percent of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 40-65% of polyalcohol and 40-65% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 20 to 65 percent of acrylic ester monomer, 0 to 15 percent of vinyl monomer, 20 to 50 percent of hydroxy acrylic ester monomer, 10 to 15 percent of organic solvent C and 0.5 to 3 percent of initiator.
In some preferred embodiments, the weight ratio of the copolymerization mixture to water is (1.1-1.2): 1.
in some preferred embodiments, the copolymerization mixture comprises, in weight percent of the copolymerization mixture: 16 to 20 percent of polyisocyanate, 3.4 to 4.5 percent of hydrophilic chain extender, 21 to 44 percent of polyester prepolymer, 0.22 to 0.45 percent of micromolecular chain extender, 9 to 29 percent of hydroxy acrylic acid prepolymer, 16 to 19 percent of organic solvent A, 6 to 7 percent of organic solvent B, 0.06 to 0.08 percent of catalyst and 2.5 to 4.5 percent of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 42-64% of polyalcohol and 42-64% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 25 to 60 percent of acrylic ester monomer, 0 to 10 percent of vinyl monomer, 24 to 49.5 percent of hydroxy acrylic ester monomer, 12 to 14.5 percent of organic solvent C and 0.8 to 2.8 percent of initiator.
In some preferred embodiments, the polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated phenyl methane diisocyanate, and hexacyclohexyl diisocyanate.
In some preferred embodiments, the polyisocyanate is selected from isophorone diisocyanate or hydrogenated phenyl methane diisocyanate. The volume of benzene ring or aliphatic ring in the molecular structure of isophorone diisocyanate or hydrogenated phenyl methane diisocyanate is large, and covalent bond mixed network structure is easily generated by polymerization reaction with polyester prepolymer, so that the hybrid network structure is formed.
In order to improve the dispersibility of the hybrid polyurethane dispersion, in some preferred embodiments, the hydrophilic chain extender is selected from at least one of dimethylolpropionic acid and dimethylolbutyric acid. Dimethylol propylene and Dimethylol butyric acidTo introduce acidic groups into polyurethane molecules, the acidic groups being hydrophilic groups, thereby improving the dispersibility of the polyurethane in water. The applicant has unexpectedly found that when the weight ratio of polyisocyanate to hydrophilic chain extender is (3-6): 1 can further improve the stability, and carboxyl anions (-COO) on the molecular chain when the content of the hydrophilic chain extender is low - ) The content is low, and the dispersibility of the hybrid polyurethane dispersion is poor; when the content of the hydrophilic chain extender is too high, carboxyl anions (-COO) on the molecular chain - ) The content is too high, the hydrophilicity of polymer particles formed by dispersion is strong, the particles of the dispersion are large, and aggregation is easy to occur.
In some preferred embodiments, the small molecule chain extender is selected from one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanediol, diethylene glycol, and trimethylolpropane.
In some preferred embodiments, the organic solvent a is selected from one or more of acetone, methyl ethyl ketone.
In some preferred embodiments, the organic solvent B is selected from one or more combinations of N-methylpyrrolidone and N-ethylpyrrolidone.
In some preferred embodiments, the catalyst is selected from at least one of diisobutyltin dilaurate, dibutyltin, stannous octoate.
In some preferred embodiments, the neutralizing agent is selected from at least one of an organic amine and a water-soluble inorganic base; preferably, the neutralizing agent is an organic amine.
In some preferred embodiments, the organic amine is selected from at least one of dimethylethanolamine, methylethanolamine, triethylamine, and triethanolamine.
In order to reduce the catalysis of the ammonium carboxylate salt on NCO side reactions, improve the stability of the hybrid polyurethane dispersion and ensure good water dispersibility of the hybrid polyurethane dispersion, in some preferred embodiments, the neutralizing agent is triethylamine, the triethylamine is strong in alkalinity and is easy to neutralize with carboxyl groups to form salts, and the triethylamine does not contain-OH, so that the triethylamine does not react with NCO and does not influence the water dispersibility of the hybrid polyurethane dispersion.
In order to increase the degree of neutralization of the hydrophilic chain extender by the neutralizing agent, in some preferred embodiments, the molar ratio of neutralizing agent to hydrophilic chain extender is (1.01-1.1): 1.
in some preferred embodiments, the polyol is selected from at least one of neopentyl glycol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, trimethylol propane, trimethylol ethane, pentaerythritol, and glycerol.
In some preferred embodiments, the polyacid is selected from at least one of isophthalic acid, adipic acid, terephthalic acid, and fumaric acid.
In some preferred embodiments, the weight ratio of the polyol to the polyacid is (0.3 to 1.6): 1.
in some preferred embodiments, the acid value of the polyester prepolymer is from 3 to 5mgKOH/g.
In some preferred embodiments, the polyester prepolymer has a number average molecular weight of 500 to 3000, preferably 1000 to 2000.
In some preferred embodiments, the weight ratio of polyester prepolymer to polyisocyanate is (1-5): 1.
in the invention, the applicant finds that the adhesive force and the flexibility of a water-based coiled material white top paint film prepared by the hybrid polyurethane dispersion can be obviously improved by adopting a polyester prepolymer with an acid value of 3-5 mgKOH/g and a number average molecular weight of 1000-2000 in the research process, and the applicant guesses that: the polyester prepolymer with the acid value of 3-5 mgKOH/g can improve the cohesive strength of the hybridized polyurethane water dispersion, thereby improving the adhesive force and the flexibility of the water-based coiled material white top paint film; the number average molecular weight of the polyester prepolymer is 1000-2000, so that the excessive viscosity of the hybridized polyurethane water dispersion can be avoided.
In some preferred embodiments, the acrylate monomer is selected from at least one of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate.
In some preferred embodiments, the acrylate monomers are methyl methacrylate and n-butyl acrylate.
In order to increase the hardness and acid and alkali resistance of the aqueous coil white top coating film prepared from the hybrid polyurethane dispersion, in some preferred embodiments, the weight ratio of methyl methacrylate to n-butyl acrylate is (0.5-2): 1. with the increase of the methyl methacrylate content, the cohesive energy and strength of the hybrid polyurethane aqueous dispersion system are increased, so that the hardness and acid and alkali resistance of the paint film of the water-based coiled material white top paint are improved.
In some preferred embodiments, the vinyl monomer is selected from at least one of styrene, vinyl toluene, alpha-methyl styrene.
In some preferred embodiments, the hydroxy acrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.
In some preferred embodiments, the organic solvent C is selected from at least one of acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N-ethylpyrrolidone.
In some preferred embodiments, the initiator is selected from at least one of t-butyl peroxy-2-ethylhexyl, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, and t-amyl peroxybenzoate.
In some preferred embodiments, the acrylic acid prepolymer has an acid value of 0 to 3mgKOH/g.
In some preferred embodiments, the acrylic prepolymer has a number average molecular weight of 3000 to 10000, preferably 4000 to 6000.
In some preferred embodiments, the weight ratio of acrylic prepolymer to polyisocyanate is (0.4-2): 1. as the amount of the acrylic prepolymer added increases, the number average molecular weight of the hybrid polyurethane dispersion increases, the viscosity of the hybrid polyurethane dispersion increases, and the water dispersibility becomes poor, resulting in poor compatibility of the hybrid polyurethane dispersion in the coating, thereby affecting the final properties of the aqueous coil white top-coat coating.
In a second aspect, the invention provides a method for preparing a hybrid polyurethane dispersion, comprising the steps of:
(1) Reacting polyalcohol and polybasic acid to obtain polyester prepolymer;
(2) Carrying out free radical polymerization on an acrylic ester monomer, an ethylene monomer, a hydroxy acrylic ester monomer and an initiator in an organic solvent C to obtain a hydroxy acrylic acid prepolymer;
(3) Mixing a hydrophilic chain extender, an organic solvent A, an organic solvent B, polyisocyanate, a polyester prepolymer, a micromolecular chain extender, a hydroxyl acrylic acid prepolymer and a catalyst for reaction, and neutralizing with a neutralizing agent to obtain a copolymerization mixture;
(4) And (3) uniformly dispersing the copolymerization mixture and water, and distilling to remove the organic solvent A to obtain the aqueous hybrid polyurethane dispersion.
The step (1) specifically comprises the following steps: adding polybasic acid and polyhydric alcohol into a reaction container, heating to 200-230 ℃, and then preserving heat and stirring until the acid value of a reaction system reaches 3-5 mgKOH/g, thus obtaining the polyester prepolymer.
The step (2) specifically comprises: adding an organic solvent C into a reaction container, uniformly dripping a mixture containing acrylate monomers, vinyl monomers, hydroxy acrylate monomers and an initiator into the reaction container, controlling the temperature in the reaction container to be 120-130 ℃, dripping for 3-5 h, and reacting at 120-130 ℃ for 2-5 h after dripping to obtain the acrylic acid prepolymer.
The step (3) specifically comprises: sequentially adding a hydrophilic chain extender, an organic solvent A and an organic solvent B, heating to 40-50 ℃ for dissolution, adding 30-90% of polyisocyanate, reacting to NCO at 65-85 ℃ to a theoretical value, adding the polyester prepolymer obtained in the step (1) and the small molecule chain extender for reacting to NCO of 0.2-0.4%, adding the acrylic prepolymer obtained in the step (2), the rest polyisocyanate and the catalyst, reacting to NCO of 0.2-0.4 at 55-75 ℃, cooling to 40-50 ℃, and adding a neutralizer for salifying to obtain a copolymer mixture.
The step (4) specifically comprises: uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 20-30 min, and distilling under reduced pressure at 50-60 ℃ to remove the organic solvent A, thus obtaining the hybrid polyurethane dispersion.
The applicant has found that the reaction temperature should not be too high when the acrylic prepolymer, the remaining polyisocyanate and the catalyst are added, and that the heterocyclic polyurethane dispersion prepared has excellent properties for coating applications, probably because the catalyst forms catalytically active sites with the polyisocyanate more easily at 55 to 75 c, and the acrylic prepolymer reacts with the polyisocyanate more easily.
The applicant has unexpectedly found that when polyisocyanate is added separately, the prepared heterocyclic polyurethane dispersion is used for preparing the water-based coiled material white finish paint, the comprehensive performance of the water-based coiled material white finish paint can be improved, and the separate addition can ensure that the polyester prepolymer can fully react with the polyisocyanate and can also ensure the full reaction of the acrylic prepolymer and the polyisocyanate.
In some preferred embodiments, the final organic solvent content is from 5 to 7% and the solids content is not less than 38%.
In a third aspect, the invention provides the use of a hybrid polyurethane dispersion for the preparation of an aqueous coating.
The fourth aspect of the invention provides a water-based baking paint coating, which comprises the following raw materials in parts by weight: 50-95 parts of hybrid polyurethane dispersoid and 5-50 parts of cross-linking agent.
In some preferred embodiments, the crosslinking agent is selected from one or more combinations of aqueous amino resins and hydrophilic blocked polyisocyanates.
In some preferred embodiments, the aqueous stoving varnish coating further comprises an adjuvant; the weight part of the auxiliary agent in the water-based baking paint coating is 0.01-10 parts; the auxiliary agent comprises at least one of wetting agent, dispersing agent, leveling agent, defoaming agent, thickening agent, pigment filler, neutralizing agent, anti-settling agent and anti-flash rust agent.
Further preferably, the wetting agent is an alkyl modified polyether; the thickener is nonionic polyurethane thickener; the pigment and filler is an inorganic pigment; the inorganic pigment is at least one selected from titanium dioxide, ferric oxide, carbon black, silver powder and aluminum powder.
In some preferred embodiments, the aqueous stoving varnish coating further comprises an organic solvent D; the weight part of the organic solvent D in the water-based baking paint coating is 1-15 parts, and more preferably 2-10 parts.
In some preferred embodiments, the organic solvent D is selected from alcohol ether solvents; the alcohol ether solvent comprises at least one of ethanol, n-butanol, isobutanol, ethylene glycol butyl ether, propylene glycol methyl ether, diethylene glycol butyl ether and dipropylene glycol butyl ether.
The beneficial effects are that:
1. the invention adopts the polyester prepolymer with the acid value of 3-5 mgKOH/g and the number average molecular weight of 1000-2000, which can obviously improve the adhesive force and the flexibility of the water-based coiled material white finish paint film prepared by the hybridization polyurethane dispersoid.
2. In the invention, when the weight ratio of the polyisocyanate to the hydrophilic chain extender is (3-6): the stability of the hybrid polyurethane dispersion can be remarkably improved in the process 1.
3. When the polyisocyanate is added separately in the preparation of the hybrid polyurethane dispersoid, the invention can ensure that the polyester prepolymer can fully react with the polyisocyanate and can also ensure that the acrylic acid prepolymer fully reacts with the polyisocyanate.
4. The functional polyester prepolymer and the acrylic acid prepolymer are hybridized and introduced into the polyurethane dispersion, and the prepared hybridized polyurethane dispersion has excellent comprehensive performance and can be used for preparing water-based coiled material coating.
5. The hybridized polyester dispersoid prepared by the invention is used for water-based coiled material coating, so that the coating has the characteristics of high gloss, good fullness, good impact resistance and good flexibility, and also has excellent hardness, acid and alkali resistance, solvent resistance and salt fog resistance.
Detailed Description
Example 1
Example 1 provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 16.8% of polyisocyanate, 3.6% of hydrophilic chain extender, 40.3% of polyester prepolymer, 0.22% of small molecule chain extender, 11.5% of acrylic acid prepolymer, 18.5% of organic solvent A, 6.2% of organic solvent B, 0.08% of catalyst and 2.8% of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 47% of polyalcohol and 53% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 60.2% of acrylic ester monomer, 24.5% of hydroxy acrylic ester monomer, 14.3% of organic solvent C and 1% of initiator.
The hydrophilic chain extender is dimethylolpropionic acid (CAS number 4767-03-7).
The polyisocyanate is isophorone diisocyanate (CAS number: 4098-71-9).
The small molecule chain extender is trimethylol propane (CAS number: 77-99-6).
The organic solvent A is acetone (CAS number 67-64-1).
The organic solvent B is N-methyl pyrrolidone (CAS number: 872-50-4).
The catalyst was diisobutyltin dilaurate (CAS number: 77-58-7).
The neutralizing agent is triethylamine (CAS number: 121-44-8).
The polyol is neopentyl glycol (CAS number: 126-30-7) and 1, 6-hexanediol (CAS number: 629-11-8), and the weight ratio is 1.3:1.
the polybasic acid is isophthalic acid (CAS number: 100-21-0) and adipic acid (CAS number: 124-04-9), and the weight ratio is 1.14:1.
the acrylic monomer is methyl methacrylate (CAS number: 80-62-6) and n-butyl acrylate (CAS number: 97-88-1), and the weight ratio is 0.72:1.
the hydroxy acrylic ester monomer is hydroxyethyl acrylate (CAS number: 818-61-1).
The organic solvent C is methyl isobutyl ketone (CAS number: 108-10-1).
The initiator is tert-butyl peroxy-2-ethylhexyl (CAS number: 3006-82-4).
The weight ratio of the copolymerization mixture to water is 1.1:1.
a method of preparing a hybrid polyurethane dispersion comprising the steps of:
(1) Neopentyl glycol, 1, 6-hexanediol, isophthalic acid and adipic acid are added into a reaction vessel, the temperature is raised to 210 ℃, and then the mixture is stirred at a temperature which is kept constant until the acid value of the reaction system reaches 4mgKOH/g, so as to obtain a polyester prepolymer with a hydroxyl value of 105mKOH/g and a number average molecular weight of 1060.
(2) Methyl isobutyl ketone is added into a reaction vessel, a mixture containing methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and tert-butyl peroxy 2-ethylhexyl acid is dripped into the reaction vessel at a constant speed, the temperature in the reaction vessel is controlled to be 125 ℃, the dripping time is controlled to be 4 hours, and the reaction is carried out for 2 hours at the temperature of 125 ℃ after the dripping is finished, so that an acrylic acid prepolymer with the hydroxyl value of 138mKOH/g and the number average molecular weight of 5643 is obtained.
(3) Sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding 80% of isophorone diisocyanate in percentage by weight of the formula, reacting at 75 ℃ until NCO is 6.8%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2), the rest of isophorone diisocyanate and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, and adding triethylamine for neutralization to form a salt, thereby obtaining a copolymer mixture.
(4) Uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 30min, and distilling under reduced pressure at 56 ℃ to remove acetone, so as to obtain the hybrid polyurethane dispersion.
Example 2
Example 2 provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 17.8% of polyisocyanate, 3.6% of hydrophilic chain extender, 22.3% of polyester prepolymer, 0.22% of small molecule chain extender, 28.5% of acrylic acid prepolymer, 18.5% of organic solvent A, 6.2% of organic solvent B, 0.08% of catalyst and 2.8% of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 60% of polyalcohol and 40% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 57% of acrylic ester monomer, 27.7% of hydroxy acrylic ester monomer, 14.3% of organic solvent C and 1% of initiator.
The hydrophilic chain extender is dimethylolpropionic acid.
The polyisocyanate is isophorone diisocyanate.
The small molecule chain extender is trimethylolpropane.
The organic solvent A is acetone.
The organic solvent B is N-methyl pyrrolidone.
The catalyst is diisobutyltin dilaurate.
The neutralizing agent is triethylamine.
The polyol is neopentyl glycol, ethylene glycol (CAS number: 107-21-1) and 1, 4-butanediol (110-63-4), and the weight ratio is 1.5:1:1.2.
the polybasic acid is adipic acid.
The acrylic ester monomer is methyl methacrylate and n-butyl acrylate, and the weight ratio is 0.72:1.
the hydroxy acrylic ester monomer is hydroxypropyl acrylate (CAS number: 25584-83-2).
The organic solvent C is methyl isobutyl ketone.
The initiator is tert-butyl peroxy-2-ethylhexyl.
The weight ratio of the copolymerization mixture to water is 1.1:1.
a method of preparing a hybrid polyurethane dispersion comprising the steps of:
(1) Neopentyl glycol, 1 ethylene glycol, 1, 4-butanediol and adipic acid are added into a reaction vessel, after the temperature is raised to 210 ℃, the mixture is stirred at a temperature until the acid value of a reaction system reaches 4mgKOH/g, and a polyester prepolymer with a hydroxyl value of 114mKOH/g and a number average molecular weight of 980 is obtained.
(2) Methyl isobutyl ketone is added into a reaction vessel, a mixture containing methyl methacrylate, n-butyl acrylate, hydroxypropyl acrylate and tert-butyl peroxy 2-ethylhexyl acid is dripped into the reaction vessel at a constant speed, the temperature in the reaction vessel is controlled to be 125 ℃, the dripping time is controlled to be 4 hours, and the reaction is carried out for 2 hours at the temperature of 125 ℃ after the dripping is finished, so that an acrylic acid prepolymer with the hydroxyl value of 138mKOH/g and the number average molecular weight of 6276 is obtained.
(3) Sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding 60% of isophorone diisocyanate in percentage by weight of the formula, reacting at 75 ℃ until NCO is 4.5%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2), the rest of isophorone diisocyanate and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, and adding triethylamine for neutralization to form a salt, thereby obtaining a copolymer mixture.
(4) Uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 30min, and distilling under reduced pressure at 56 ℃ to remove acetone, so as to obtain the hybrid polyurethane dispersion.
Example 3
Example 3 provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 21.4% of polyisocyanate, 3.6% of hydrophilic chain extender, 37.2% of polyester prepolymer, 0.22% of small molecule chain extender, 10% of acrylic acid prepolymer, 18.5% of organic solvent A, 6.2% of organic solvent B, 0.08% of catalyst and 2.8% of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 42% of polyalcohol and 58% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 25% of acrylic monomer, 10.2% of vinyl monomer, 49.5% of hydroxy acrylic monomer, 14.3% of organic solvent C and 1% of initiator.
The hydrophilic chain extender is dimethylolpropionic acid.
The polyisocyanate is hydrogenated phenyl methane diisocyanate (CAA No. 5124-30-1).
The small molecule chain extender is trimethylolpropane.
The organic solvent A is acetone.
The organic solvent B is N-methyl pyrrolidone.
The catalyst is diisobutyltin dilaurate.
The neutralizing agent is triethylamine.
The polyol is diethylene glycol (CAS number: 111-46-6) and propylene glycol (CAS number: 57-55-6), and the weight ratio is 1.2:1.
the polybasic acid is isophthalic acid and adipic acid, and the weight ratio is 1.2:1.
the acrylic ester monomer is methyl methacrylate and n-butyl acrylate, and the weight ratio is 0.72:1.
the ethylene monomer is styrene (CAS number: 100-42-5).
The hydroxy acrylic ester monomer is hydroxyethyl acrylate.
The organic solvent C is methyl isobutyl ketone.
The initiator is tert-butyl peroxy-2-ethylhexyl.
The weight ratio of the copolymerization mixture to water is 1.1:1.
a method of preparing a hybrid polyurethane dispersion comprising the steps of:
(1) Diethylene glycol, propylene glycol, isophthalic acid and adipic acid are added into a reaction vessel, the temperature is raised to 210 ℃, and then the mixture is stirred at a temperature until the acid value of the reaction system reaches 4mgKOH/g, so as to obtain a polyester prepolymer, the hydroxyl value of which is 110mKOH/g, and the number average molecular weight of which is 1000.
(2) Adding methyl isobutyl ketone into a reaction vessel, uniformly dripping a mixture containing methyl methacrylate, styrene, n-butyl acrylate, hydroxyethyl acrylate and tert-butyl peroxy 2-ethylhexyl into the reaction vessel, controlling the temperature in the reaction vessel to be 125 ℃, controlling the dripping time to be 4 hours, and reacting at 125 ℃ for 2 hours after the dripping is finished to obtain an acrylic acid prepolymer with the hydroxyl value of 279mKOH/g and the number average molecular weight of 6854.
(3) Sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding 46% hydrogenated phenyl methane diisocyanate in percentage by weight of the formula, reacting at 75 ℃ until NCO is 2.5%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2), the residual hydrogenated phenyl methane diisocyanate and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, and adding triethylamine for neutralization to form salt, thus obtaining a copolymerization mixture.
(4) Uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 30min, and distilling under reduced pressure at 56 ℃ to remove acetone, so as to obtain the hybrid polyurethane dispersion.
Example 4
Example 4 provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 15.4% of polyisocyanate, 3.6% of hydrophilic chain extender, 43.3% of polyester prepolymer, 0.22% of small molecule chain extender, 9.9% of acrylic acid prepolymer, 18.5% of organic solvent A, 6.2% of organic solvent B, 0.08% of catalyst and 2.8% of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 45.8% of polyalcohol and 54.2% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 60.2% of acrylic ester monomer, 24.5% of hydroxy acrylic ester monomer, 14.3% of organic solvent C and 1% of initiator.
The hydrophilic chain extender is dimethylolpropionic acid.
The polyisocyanate is hydrogenated phenyl methane diisocyanate.
The small molecule chain extender is trimethylolpropane.
The organic solvent A is acetone.
The organic solvent B is N-methyl pyrrolidone.
The catalyst is diisobutyltin dilaurate.
The neutralizing agent is triethylamine.
The polyol is neopentyl glycol and 1, 6-hexanediol, and the weight ratio is 1.2:1.
the polybasic acid is adipic acid.
The acrylic ester monomer is methyl methacrylate and n-butyl acrylate, and the weight ratio is 0.72:1.
the hydroxy acrylic ester monomer is hydroxyethyl acrylate.
The organic solvent C is methyl isobutyl ketone.
The initiator is tert-butyl peroxy-2-ethylhexyl.
The weight ratio of the copolymerization mixture to water is 1.1:1.
a method of preparing a hybrid polyurethane dispersion comprising the steps of:
(1) Neopentyl glycol, 1, 6-hexanediol and adipic acid are added into a reaction vessel, after the temperature is raised to 210 ℃, the mixture is stirred at a temperature until the acid value of a reaction system reaches 4mgKOH/g, and a polyester prepolymer with a hydroxyl value of 54mKOH/g and a number average molecular weight of 2070 is obtained.
(2) Methyl isobutyl ketone is added into a reaction vessel, a mixture containing methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and tert-butyl peroxy 2-ethylhexyl acid is dripped into the reaction vessel at a constant speed, the temperature in the reaction vessel is controlled to be 125 ℃, the dripping time is controlled to be 4 hours, and the reaction is carried out for 2 hours at the temperature of 125 ℃ after the dripping is finished, so that an acrylic acid prepolymer with the hydroxyl value of 139mKOH/g and the number average molecular weight of 5968 is obtained.
(3) Sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding 56% hydrogenated phenyl methane diisocyanate in percentage by weight of the formula, reacting at 75 ℃ until NCO is 4.3%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2), the residual hydrogenated phenyl methane diisocyanate and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, and adding triethylamine for neutralization to form salt, thus obtaining a copolymerization mixture.
(4) Uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 30min, and distilling under reduced pressure at 56 ℃ to remove acetone, so as to obtain the hybrid polyurethane dispersion.
Example 5
Example 5 provides a hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 19.9% of polyisocyanate, 3.6% of hydrophilic chain extender, 28.5% of polyester prepolymer, 0.22% of small molecule chain extender, 20.2% of acrylic acid prepolymer, 18.5% of organic solvent A, 6.2% of organic solvent B, 0.08% of catalyst and 2.8% of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 56.8% of polyol and 43.2% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 25% of acrylic monomer, 10.2% of vinyl monomer, 49.5% of hydroxy acrylic monomer, 14.3% of organic solvent C and 1% of initiator.
The hydrophilic chain extender is dimethylolpropionic acid.
The polyisocyanate is isophorone diisocyanate.
The small molecule chain extender is trimethylolpropane.
The organic solvent A is acetone.
The organic solvent B is N-methyl pyrrolidone.
The catalyst is diisobutyltin dilaurate.
The neutralizing agent is triethylamine.
The polyol is diethylene glycol, ethylene glycol and 1, 4-butanediol, and the weight ratio is 1.3:1:1.3.
the polybasic acid is isophthalic acid and adipic acid, and the weight ratio is 0.9:1.
the acrylic ester monomer is methyl methacrylate and n-butyl acrylate, and the weight ratio is 1.5:1.
the hydroxy acrylic ester monomer is hydroxyethyl acrylate.
The organic solvent C is methyl isobutyl ketone.
The initiator is tert-butyl peroxy-2-ethylhexyl.
The weight ratio of the copolymerization mixture to water is 1.1:1.
a method of preparing a hybrid polyurethane dispersion comprising the steps of:
(1) Neopentyl glycol, 1, 6-hexanediol, isophthalic acid and adipic acid are added into a reaction vessel, the temperature is raised to 210 ℃, and then the mixture is stirred at a temperature which is kept constant until the acid value of the reaction system reaches 4mgKOH/g, so as to obtain a polyester prepolymer, the hydroxyl value of which is 56mKOH/g, and the number average molecular weight of which is 1988.
(2) Methyl isobutyl ketone is added into a reaction vessel, a mixture containing methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and tert-butyl peroxy 2-ethylhexyl acid is dripped into the reaction vessel at a constant speed, the temperature in the reaction vessel is controlled to be 125 ℃, the dripping time is controlled to be 4 hours, and the reaction is carried out for 2 hours at the temperature of 125 ℃ after the dripping is finished, so that an acrylic acid prepolymer with the hydroxyl value of 280mKOH/g and the number average molecular weight of 6239 is obtained.
(3) Sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding 80% of isophorone diisocyanate in percentage by weight of the formula, reacting at 75 ℃ until NCO is 6.8%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2), the rest of isophorone diisocyanate and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, and adding triethylamine for neutralization to form a salt, thereby obtaining a copolymer mixture.
(4) Uniformly dispersing the copolymerization mixture obtained in the step (3) and water, stirring for 30min, and distilling under reduced pressure at 56 ℃ to remove acetone, so as to obtain the hybrid polyurethane dispersion.
Example 6
Example 6 provides a hybrid polyurethane dispersion, the embodiment of which is the same as example 1, except that the polyisocyanate is 14.8 weight percent; the weight percentage of the hydrophilic chain extender is 5.6%.
Example 7
Example 7 provides a hybrid polyurethane dispersion, which is similar to example 1 in its specific embodiment, except that step (3) is: sequentially adding dimethylolpropionic acid, acetone and N-methylpyrrolidone, heating to 45 ℃ for dissolution, adding isophorone diisocyanate, reacting at 75 ℃ until NCO is 6.8%, adding the polyester prepolymer obtained in the step (1) and trimethylolpropane for reaction until NCO is 0.3%, adding the acrylic acid prepolymer obtained in the step (2) and diisobutyltin dilaurate, reacting at 65 ℃ until NCO is 0.3%, cooling to 45 ℃, adding triethylamine for neutralization to form salt, and obtaining a copolymerization mixture.
Comparative example 1
Comparative example 1 provides a conventional oily hydroxy acrylic resin, the preparation method of which comprises the following steps:
(1) 1200g of dimethylbenzene is added into a reaction vessel, the monomer mixture is dripped into the reaction vessel at a constant speed, the temperature in the reaction vessel is controlled to be 125 ℃, the dripping time is 4 hours, and the reaction is carried out for 2 hours at the temperature of 125 ℃ after the dripping is finished, so that the conventional oily hydroxy acrylic resin is obtained;
in step (1), the monomer mixture consists of the following components: 450g of methyl methacrylate, 500g of styrene, 1450g of n-butyl acrylate, 1000g of hydroxyethyl methacrylate and 50g of tert-butyl peroxybenzoate.
Comparative example 2
Comparative example 2 provides a conventional oily hydroxyl polyester resin, the preparation method of which comprises the following steps:
1140g of neopentyl glycol, 760g of 1, 6-hexanediol, 70g of trimethylolpropane, 1000g of isophthalic acid and 1030g of adipic acid are added into a reaction vessel, after the temperature is raised to 210 ℃, the temperature is kept and stirred until the acid value of the reaction system reaches 4mgKOH/g, the temperature is reduced to 100 ℃, 1000g of dimethylbenzene is added for dilution, and the conventional oily hydroxyl polyester resin is obtained after uniform stirring.
Application example 1
Application example 1 provides an aqueous coil white top-coat paint comprising a hybrid polyurethane dispersion and a cross-linking agent.
The preparation method comprises the following steps:
(1) Weighing the following raw materials in parts by weight: 4.5 parts of deionized water, 1 part of a dispersing agent Tego755W, 0.1 part of N, N-dimethylethanolamine, 20 parts of titanium dioxide, 0.2 part of a wetting agent Surfynol104BC, 0.2 part of a defoaming agent Tego902W and 1 part of a 10% aqueous solution of an anti-settling agent BYK420, and uniformly stirring after mixing, and standing for 30min to obtain aqueous white paste;
(2) The following raw materials in parts by weight are sequentially added into the water-based white paste: 50 parts of hybrid polyurethane dispersoid, 0.1 part of N, N-dimethylethanolamine, 8.8 parts of deionized water, 11.4 parts of cross-linking agent, 2 parts of diethylene glycol butyl ether, 0.1 part of defoaming agent Tego902W, 0.3 part of wetting agent Tego and 0.3 part of thickening agent U605, and uniformly dispersing to obtain a water-based baking paint coating;
the hybrid polyurethane dispersion was prepared as in example 1.
The cross-linking agent is a blocked polyisocyanate and an amino resin, and the weight ratio is 0.7:1, a step of; the blocked polyisocyanate is Deshi mouldBL 3175SN; the amino resin is CYMEL303 LF resin. />
Application example 2
Application example 2 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 2.
Application example 3
Application example 3 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 3.
Application example 4
Application example 4 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 4.
Application example 5
Application example 5 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 5.
Application example 6
Application example 6 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 6.
Application example 7
Application example 7 provides an aqueous coiled material white top-coat paint, and a specific embodiment is the same as application example 1, except that the hybrid polyurethane dispersion adopted in the application example is prepared in example 7.
Application example 8
Application example 8 provides an oily coiled material white finish paint, and the preparation method comprises the following steps:
(1) Weighing the following raw materials in parts by weight: 4.8 parts of dimethylbenzene, 1 part of dispersant BYK191, 20 parts of titanium pigment, 0.2 part of defoamer BYK028 and 1 part of 10% aqueous solution of anti-settling agent BYK420 are mixed, stirred uniformly and stood for 30min to obtain oily white paste;
(2) The following raw materials in parts by weight are sequentially added into the oily white paste: 30 parts of oily hydroxyl acrylic resin, 15 parts of butyl acetate, 17.6 parts of n-butyl alcohol, 303 parts of amino resin CYMEL, 0280.2 parts of defoamer BYK and 270.2 parts of wetting agent Tego, and uniformly dispersing to obtain an oily baking paint coating;
the oily hydroxyacrylic resin was prepared from comparative example 1.
Application example 9
Application example 9 provides an oily coiled material white top-coat paint, and the specific embodiment is the same as application example 6, except that the oily hydroxyl polyester resin adopted in the application example is prepared from comparative example 2.
Performance testing
1. The products prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to characterization tests as follows:
(1) The appearance of each sample was observed by visual inspection;
(2) Taking 1g of sample, drying at 125 ℃ for 1h, detecting the weight of the dried sample, and calculating the content of non-volatile matters in the sample;
(3) Testing the viscosity of each sample using a rotational viscometer in an environment at 25 ℃;
(4) Detecting the acid value of the sample by adopting a titration method, and further testing the OH content relative to 100% of solid;
(5) Detecting the average particle size of the sample by using a laser particle sizer;
(6) Samples were mixed with deionized water according to 1:4, after the mass ratio is diluted, detecting the pH value of the diluted sample by using a pH meter;
(7) The samples were placed in a 50 ℃ dry box and after 30 days of storage, the appearance of the samples was observed.
The test results are shown in Table 1.
2. The water-based coiled material baking paint coating prepared in each application example is constructed by the following construction method:
and (3) selecting galvanized steel plates with the thickness of 30cm multiplied by 16cm multiplied by 0.5cm, respectively coating the prepared coatings on the steel plates by using 28# bars, quickly putting the steel plates into a 320 ℃ high-temperature oven for baking for 25-30 seconds (the plate temperature PMT is 232-249 ℃), quickly taking out, and cooling to prepare a paint film template.
The performance characterization test is carried out on the coating film obtained by construction, the result is shown in table 2, and the test method is as follows:
(1) Viscosity (DIN 4 cup, 25 ℃ C.) test: the test was performed according to GB/T1723-79 using a paint-4 cup test manufactured by Guangzhou Bidada, inc.
(2) Gloss (20/60 °) test: the test was carried out according to GB/T9754-98 using a BGD 516/2 dual angle gloss meter manufactured by Guangzhou Bidada limited.
(3) Paint film thickness test: a BGD 542/2 precision coating thickness gauge manufactured by Guangzhou Bidada Co., ltd was used.
(4) Curing time: the time for the paint film to enter the oven to dry completely was tested.
(5) Adhesion/repainting adhesion (hundred method)/grade: measured according to the method of GB/T9286-1998, the BGD502 test produced by Guangzhou Bidada Co., ltd
(6) Pencil hardness: the combined pencil hardness tester of BGD 505 produced by Guangzhou Bidada Co., ltd was used for measurement according to the method of GB/T6739-2006.
(7) Impact resistance/cm: the film impactor test was carried out according to GB/T1732-93, using BGD 304 paint film impactor manufactured by Guangzhou Bida limited.
(8) Flexibility test (T-bend): measured according to the method of GB/T30791, and tested by using a BGD 568-T bending machine manufactured by Guangzhou Bidada limited company.
(9) Salt spray resistance/h: after the sample plate is sealed by using a model 600 adhesive tape of 3M company at room temperature (25 ℃) according to the measurement of GB/T1771-91 method, two breaking lines with an angle of 60 DEG are crossed and cut by a blade in the middle of the sample plate, the coating is cut, a paint film is observed, and the corrosion time is recorded.
(10) Acid resistance test/h: the foaming time was recorded after the panels were sealed with a model 600 tape from 3M company at room temperature (25 ℃) as determined by GB/T9274-88.
(11) Alkali resistance test/h: the film was observed at room temperature (25 ℃) by measuring according to GB/T9274-88 method, sealing the edges of the sample plate with a model 600 adhesive tape of 3M company, immersing in a NaOH solution with a mass concentration of 0.1M, and recording the foaming time.
(12) MEK rub resistance/number: the test is carried out according to the GB/T23989-2009 method, and a BGD 521 multifunctional coating solvent resistance tester produced by Guangzhou Bidada limited company is adopted for testing.
Test results
Table 1:
TABLE 2
The results in table 2 above show that: compared with application examples 8 and 9, the application examples 1 to 5 of the invention add the hybridized polyurethane dispersion into the water-based coil baking varnish, and the coating layer has the characteristics of high gloss, good fullness, good impact resistance, good flexibility and good adhesive force due to the action of polyurethane and polyester components, and in addition, the water-based coil baking varnish of the application examples 1 to 5 has excellent hardness, acid and alkali resistance, solvent resistance and salt spray resistance due to the action of acrylic acid components.

Claims (10)

1. A hybrid polyurethane dispersion comprising a copolymerization mixture and water; the copolymer mixture comprises, in weight percent of the copolymer mixture: 15 to 22 percent of polyisocyanate, 3 to 5 percent of hydrophilic chain extender, 20 to 45 percent of polyester prepolymer, 0.2 to 0.5 percent of small molecule chain extender, 8 to 30 percent of acrylic acid prepolymer, 15 to 20 percent of organic solvent A, 5 to 8 percent of organic solvent B, 0.05 to 1 percent of catalyst and 2 to 5 percent of neutralizer; the polyester prepolymer comprises, in weight percent, the following: 40-65% of polyalcohol and 40-65% of polybasic acid; the acrylic acid prepolymer comprises, in weight percent of the acrylic acid prepolymer: 20 to 65 percent of acrylic ester monomer, 0 to 15 percent of vinyl monomer, 20 to 50 percent of hydroxy acrylic ester monomer, 10 to 15 percent of organic solvent C and 0.5 to 3 percent of initiator.
2. A hybrid polyurethane dispersion according to claim 1, characterized in that the weight ratio of the copolymerization mixture to water is (1.1-1.2): 1.
3. a hybrid polyurethane dispersion according to claim 1, characterized in that the weight ratio of polyisocyanate to hydrophilic chain extender is (3-6): 1.
4. a hybrid polyurethane dispersion according to claim 1 wherein the acid value of the acrylic prepolymer is from 0 to 3mgKOH/g; the number average molecular weight of the acrylic acid prepolymer is 3000-10000.
5. A hybrid polyurethane dispersion according to claim 1, wherein the acid value of the polyester prepolymer is 3 to 5mgKOH/g; the number average molecular weight of the polyester prepolymer is 500-3000.
6. A hybrid polyurethane dispersion according to claim 1, characterized in that the molar ratio of neutralizing agent to hydrophilic chain extender is (1.01-1.1): 1.
7. a process for the preparation of a hybrid polyurethane dispersion according to any one of claims 1 to 6, comprising the steps of:
(1) Reacting polyalcohol and polybasic acid to obtain polyester prepolymer;
(2) Carrying out free radical polymerization on an acrylic ester monomer, an ethylene monomer, a hydroxy acrylic ester monomer and an initiator in an organic solvent C to obtain a hydroxy acrylic acid prepolymer;
(3) Mixing a hydrophilic chain extender, an organic solvent A, an organic solvent B, polyisocyanate, a polyester prepolymer, a micromolecular chain extender, a hydroxyl acrylic acid prepolymer and a catalyst for reaction, and neutralizing with a neutralizing agent to obtain a copolymerization mixture;
(4) And (3) uniformly dispersing the copolymerization mixture and water, and distilling to remove the organic solvent A to obtain the aqueous hybrid polyurethane dispersion.
8. Use of the hybrid polyurethane dispersion according to any one of claims 1 to 6 for the preparation of aqueous coatings.
9. An aqueous stoving varnish coating comprising a hybrid polyurethane dispersion according to any one of claims 1 to 6 and a cross-linking agent.
10. The aqueous baking paint coating of claim 9 wherein the crosslinking agent is selected from one or a combination of aqueous amino resins, hydrophilic blocked polyisocyanates.
CN202211301174.2A 2022-10-24 2022-10-24 Hybrid polyurethane dispersoid and preparation method and application thereof Pending CN116515071A (en)

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