CN112175147B - Waterborne polyurethane-polyacrylate resin and preparation method and application thereof - Google Patents
Waterborne polyurethane-polyacrylate resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112175147B CN112175147B CN202010932433.6A CN202010932433A CN112175147B CN 112175147 B CN112175147 B CN 112175147B CN 202010932433 A CN202010932433 A CN 202010932433A CN 112175147 B CN112175147 B CN 112175147B
- Authority
- CN
- China
- Prior art keywords
- parts
- mixture
- hours
- waterborne polyurethane
- polyacrylate resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a waterborne polyurethane-polyacrylate resin which is mainly obtained by the reaction of a waterborne polyurethane prepolymer, an acrylic acid monomer and an initiator, wherein the waterborne polyurethane prepolymer is obtained by the reaction of a polyol prepolymer, an isocyanate monomer, a solvent, a hydrophilic monomer, a functional monomer, a catalyst, a chain extender, an acrylic acid monomer and an organic base. The waterborne polyurethane-polyacrylate resin has extremely low VOC content, is green and environment-friendly, and simultaneously, the prepared waterborne metallic flashing paint has excellent stone impact resistance after film forming.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to a water-based polyurethane-polyacrylate resin, and a preparation method and application thereof.
Background
In recent years, with the increasing national environmental protection requirements, the water-based automobile coating becomes the development direction of the future, and no matter the intermediate coating, the colored paint layer or the clear paint layer is changed to the water-based one. Compared with the traditional solvent-based system, the water-based paint has multiple advantages, such as low VOC content, reduced process flow, energy conservation, emission reduction, cost reduction and the like. The related aqueous resins have also been rapidly developed. Among them, two resins that are attracting attention are aqueous urethane resins and polyacrylate resins. The waterborne polyurethane resin has the advantages of low VOC content, environmental protection and the like, the polyacrylate resin has the characteristics of sufficient raw material supply and low price, but when the waterborne polyurethane resin and the polyacrylate resin are respectively applied to the waterborne metallic flashing paint of an automobile, the stone impact resistance of a paint film is not good, so that the development of the resin capable of improving the stone impact resistance of the paint film of the waterborne metallic flashing paint of the automobile is urgently needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the waterborne polyurethane-polyacrylate resin and the preparation method and application thereof, and the waterborne polyurethane-polyacrylate resin has excellent stone impact resistance when being applied to the waterborne metallic flashing paint of the automobile.
The technical purpose of the invention is realized by the following technical scheme:
the waterborne polyurethane-polyacrylate resin is mainly obtained by reacting a waterborne polyurethane prepolymer, an acrylic acid monomer and an initiator, wherein the waterborne polyurethane prepolymer is obtained by reacting a polyol prepolymer, an isocyanate monomer, a solvent, a hydrophilic monomer, a functional monomer, a catalyst, a chain extender, the acrylic acid monomer and an organic base.
Preferably, the weight ratio of the waterborne polyurethane prepolymer to the acrylic monomer is (10-40): (3-16).
Preferably, the hydrophilic monomer is at least one of dihydroxy compounds, polyethylene glycol and sulfonate.
Preferably, the functional monomer is at least one of unsaturated fatty acid, glycerol, pentaerythritol, trimethylolpropane monoallyl ether and tertiary carboxylic acid glycidyl ester.
Preferably, the dihydroxy compound is at least one of dimethylolbutyric acid and dimethylolpropionic acid.
Preferably, the sulfonate is at least one of 1,4-butanediol-2-sodium sulfonate and 1,2-propanediol-3-sodium sulfonate.
Preferably, the unsaturated fatty acid is at least one of oleic acid, linoleic acid, eleostearic acid, ricinoleic acid and soybean oleic acid.
Preferably, the functional monomer comprises glycidyl versatate, and the weight ratio of the functional monomer to the hydrophilic monomer is (1-4): (1-5).
Preferably, the initiator is at least one of benzoyl peroxide, azobisisobutyronitrile, potassium persulfate, ammonium persulfate, tert-butyl peroxycarboxylate, cumene hydroperoxide, lauroyl peroxide, tert-butyl hydroperoxide and tert-amyl peroxypivalate.
Preferably, the polyol prepolymer is at least one of polyester polyol and polyether polyol.
Preferably, the isocyanate monomer is at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate trimer, diphenylmethane diisocyanate, isophorone diisocyanate trimer, tetramethylxylylene diisocyanate, xylylene diisocyanate, and cyclohexanedimethylene diisocyanate.
Preferably, the acrylic monomer is at least one of diacetone acrylamide, methyl methacrylate, butyl methacrylate, styrene, n-butyl acrylate, lauryl acrylate, acrylamide, divinyl benzene, 2-hydroxyethyl acrylate, ethyl acrylate, glycidyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl acrylate and tert-butyl acrylate.
Preferably, the catalyst is at least one of stannous chloride, monobutyl tin oxide, dibutyl tin acetate, tin dilaurate, organic bismuth, dibutyltin maleate and stannous octoate.
Preferably, the chain extender is at least one of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, hexamethylenediamine and dipropylene glycol.
Preferably, the organic base is one or more of N, N '-dimethylethanolamine, N' -diisopropylethylamine, triethylamine, triethanolamine, diisopropylamine, N-propylamine and 1,2-propanediamine; the solvent comprises at least one of butanone, ethylene glycol butyl ether, propylene glycol methyl ether acetate, butyl acetate, methyl isobutyl ketone and diethylene glycol butyl ether.
Preferably, the solvent is at least one of butanone, ethylene glycol butyl ether, propylene glycol methyl ether acetate, butyl acetate, methyl isobutyl ketone and diethylene glycol butyl ether.
Preferably, the acid value of the waterborne polyurethane-polyacrylate resin is 5-50 mg KOH/g, the viscosity is 10-1000mPa.s, the glass transition temperature is 5-80 ℃, and the solid content is 30-45%.
Another object of the present invention is to provide a method for preparing the above aqueous polyurethane-polyacrylate resin:
a preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparing a waterborne polyurethane prepolymer: under the protection of inert gas, adding a polyol prepolymer, an isocyanate monomer and a solvent into a reactor, heating, reacting, then adding a hydrophilic monomer, a functional monomer and a catalyst, reacting, then adding a chain extender, stirring, reacting, cooling, adding an acrylic acid monomer, reacting, then adding an organic base, neutralizing, then adding water under a shearing condition, and stirring to prepare a waterborne polyurethane prepolymer;
(2) Preparing the waterborne polyurethane-polyacrylate resin: under the protection of inert gas, heating the waterborne polyurethane prepolymer prepared in the step (1), dissolving an initiator in an acrylic monomer to form a mixed solution, dropwise adding the mixed solution into the waterborne polyurethane prepolymer, carrying out heat preservation reaction, cooling, and removing the solvent to obtain the waterborne polyurethane-polyacrylate resin.
A coating comprising an aqueous polyurethane-polyacrylate resin as described above.
The application of the waterborne polyurethane resin in waterborne polyurethane-polyacrylate resin in waterborne metallic flashing paint is disclosed.
The invention has the beneficial effects that:
(1) The waterborne polyurethane-polyacrylate resin disclosed by the invention has extremely low VOC content and is green and environment-friendly.
(2) The waterborne polyurethane-polyacrylate resin disclosed by the invention has excellent stone impact resistance, and the stone impact resistance grade can reach 2 and above.
(3) According to the waterborne polyurethane-polyacrylate resin, the waterborne metallic flashing paint prepared from the functional monomer and the hydrophilic monomer in a specific weight ratio has higher crosslinking density during film forming, so that the adhesive force and the stone impact resistance of a paint film can be obviously improved.
(4) The acid value of the waterborne polyurethane-polyacrylate resin is 5-50 mg KOH/g, the viscosity is 10-1000mPa.s, the glass transition temperature is 5-80 ℃, and the solid content is 30-45%, and the characteristics ensure that the waterborne metallic flashing paint has excellent weather resistance and stone-impact resistance when the waterborne polyurethane-polyacrylate resin is applied to the waterborne metallic flashing paint.
(5) According to the waterborne polyurethane-polyacrylate resin, the waterborne polyurethane prepolymer and the acrylic acid monomer are in a specific weight ratio, so that the prepared resin has good solvent responsiveness, and the resin has a thixotropic function, so that a good aluminum powder arrangement effect can be shown in the waterborne metallic flashing paint, and the weather resistance of a paint film is improved.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 403 parts of (1);
t-butyl hydroperoxide: 3 parts of a mixture;
methyl methacrylate: 12 parts of (a);
divinylbenzene: 2 parts of (1);
ethyl acrylate: 10 parts of (A);
butyl methacrylate: 15 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polyester diol: 30 parts of (1);
hexamethylene diisocyanate: 15 parts of (1);
isophorone diisocyanate: 15 parts of (1);
methyl isobutyl ketone: 15 parts of (1);
dimethylolbutyric acid: 8 parts of a mixture;
glycerol: 3 parts of a mixture;
linoleic acid: 3 parts of a mixture;
organic bismuth: 2 parts of (1);
1.6-hexanediol: 8 parts of a mixture;
acrylamide: 3 parts of a mixture;
styrene: 26 parts of:
lauryl acrylate: 10 parts of (A);
glycidyl methacrylate: 6 parts of (1);
methacrylic acid: 5 parts of a mixture;
triethylamine: 6 parts of (1);
deionized water: 248 parts of the raw materials.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparing a waterborne polyurethane prepolymer: under the protection of nitrogen, adding 30 parts of saturated polyester diol, 15 parts of hexamethylene diisocyanate, 15 parts of isophorone diisocyanate and 15 parts of methyl isobutyl ketone into a reactor, slowly raising the temperature to 85 ℃, and reacting for 2 hours; adding 8 parts of dimethylolbutyric acid, 3 parts of glycerol, 3 parts of linoleic acid and 2 parts of organic bismuth, further reacting for 2 hours at 90 ℃, adding 8 parts of 1.6-hexanediol for chain extension reaction, stirring for reaction for 1 hour, cooling, adding an acrylic acid mixed solution (3 parts of acrylamide, 26 parts of styrene, 10 parts of lauryl acrylate, 6 parts of glycidyl methacrylate and 5 parts of methacrylic acid) into a reaction kettle, stirring for 1 hour, and adding 6 parts of triethylamine for neutralization reaction. Adding 248 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparing the waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 80 ℃, dissolving 3 parts of tert-butyl hydroperoxide in an acrylic acid mixed solution (12 parts of methyl methacrylate, 2 parts of divinylbenzene, 10 parts of ethyl acrylate and 15 parts of butyl methacrylate), slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving the temperature for 3 hours after dropwise adding is finished, cooling after complete reaction, removing the solvent from the obtained resin through a reduced-pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 15 mg KOH/g, the viscosity is 850mPa.s, the vitrification temperature is 30 ℃, and the solid content is 40%.
Example 2:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 351 parts of a binder;
lauroyl peroxide: 3 parts of a mixture;
butyl methacrylate: 16 parts of a mixture;
diacetone acrylamide: 3 parts of a mixture;
ethyl acrylate: 10 parts of (A);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
unsaturated polycarbonate diol: 32 parts of (1);
cyclohexanedimethylene diisocyanate: 25 parts of (1);
hexamethylene diisocyanate trimer: 2 parts of (1);
butanone: 15 parts of (1);
polyethylene glycol: 15 parts of (1);
trimethylolpropane monoallyl ether: 8 parts of a mixture;
soybean oleic acid: 2 parts of (1);
tin dilaurate: 2 parts of (1);
hexamethylene diamine: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
n-butyl acrylate: 18 parts of:
styrene: 12 parts of (1);
t-butyl acrylate: 6 parts;
dimethylethanolamine: 4 parts of a mixture;
deionized water: 200 parts.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 32 parts of unsaturated polycarbonate diol, 25 parts of cyclohexanedimethylene diisocyanate, 2 parts of hexamethylene diisocyanate trimer and 15 parts of butanone into a reactor, slowly raising the temperature to 105 ℃, and reacting for 2 hours; adding 15 parts of polyethylene glycol, 8 parts of trimethylolpropane monoallyl ether, 2 parts of soybean oleic acid and 2 parts of tin dilaurate, further reacting for 3 hours at 95 ℃, adding 5 parts of hexamethylenediamine for chain extension reaction, stirring for reacting for 3 hours, cooling, adding an acrylic acid mixed solution (5 parts of lauryl acrylate, 18 parts of N-butyl acrylate, 12 parts of styrene and 6 parts of tert-butyl acrylate) into a reaction kettle, stirring for 2 hours, and adding 4 parts of N, N' -dimethylethanolamine for neutralization reaction. Adding 200 parts of deionized water under a high shear condition, and stirring for 1h to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, the temperature of the aqueous polyurethane prepolymer prepared in the step (1) is raised to 80 ℃, and 3 parts of lauroyl peroxide is dissolved in an acrylic acid mixed solution (16 parts of butyl methacrylate, 3 parts of diacetone acrylamide and 10 parts of ethyl acrylate). Slowly dripping the mixed solution for 3h under the stirring condition, continuing to preserve heat for 3h after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 36 mg KOH/g, the viscosity is 700mPa.s, the vitrification temperature is 35 ℃, and the solid content is 35%.
Example 3:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of a mixture;
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
tertiary carboxylic acid glycidyl ester: 3 parts of a mixture;
pentaerythritol: 2 parts of a mixture;
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of (1);
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 parts.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1, 4-butanediol-2-sodium sulfonate, 3 parts of glycidyl versatate, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1, 4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 230 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azobisisobutyronitrile into an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3h under the stirring condition, continuously preserving the heat for 4h after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 33 mg KOH/g, the viscosity is 750mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Example 4:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 464.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
glycidyl versatate: 3 parts of a mixture;
pentaerythritol: 2 parts of (1);
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of (1);
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 330 parts of (A).
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1, 4-butanediol-2-sodium sulfonate, 3 parts of glycidyl versatate, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1, 4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 330 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azobisisobutyronitrile into an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3 hours under the stirring condition, continuing to preserve heat for 4 hours after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 28 mg KOH/g, the viscosity is 600mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Example 5:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of a binder;
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of a mixture;
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 13 parts of (1);
glycidyl versatate: 1 part;
pentaerythritol: 1 part;
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of a binder;
methyl methacrylate: 15 parts of a mixture;
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 portions.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 13 parts of 1.4-butanediol-2-sodium sulfonate, 1 part of glycidyl versatate, 1 part of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1.4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of 2-hydroxyethyl acrylate) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 230 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3 hours under the stirring condition, continuously preserving the heat for 4 hours after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 35 mg KOH/g, the viscosity is 760mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Example 6:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts of (1);
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
trimethylolpropane monoallyl ether: 3 parts of a mixture;
pentaerythritol: 2 parts of (1);
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of a mixture;
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of a mixture;
deionized water: 230 parts.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1, 4-butanediol-2-sodium sulfonate, 3 parts of trimethylolpropane monoallyl ether, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1, 4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 230 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azobisisobutyronitrile into an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3 hours under the stirring condition, continuously preserving the heat for 4 hours after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 36 mg KOH/g, the viscosity is 730mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Comparative example 1:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 354.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of a binder;
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of a binder;
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts of (1);
glycidyl versatate: 3 parts of a mixture;
pentaerythritol: 2 parts of a mixture;
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of (1);
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 parts.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 3 parts of glycidyl versatate, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1.4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of 2-hydroxyethyl acrylate) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 230 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3h under the stirring condition, continuously preserving the heat for 4h after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 33 mg KOH/g, the viscosity is 750mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Comparative example 2:
the waterborne polyurethane-polyacrylate resin comprises the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 359.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of (1);
butyl methacrylate: 10 parts of:
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 portions.
The preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1, 4-butanediol-2-sodium sulfonate and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1, 4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution (15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester) into a reaction kettle, stirring for 2 hours, and adding 2 parts of N, N' -diisopropylethylamine. Adding 230 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the waterborne polyurethane prepolymer prepared in the step (1) to 90 ℃, and dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution (5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate). Slowly dripping the mixed solution for 3h under the stirring condition, continuously preserving the heat for 4h after dripping is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the waterborne polyurethane-polyacrylate resin, wherein the acid value of the waterborne polyurethane-polyacrylate resin is 33 mg KOH/g, the viscosity is 750mPa.s, the vitrification temperature is 36 ℃, and the solid content is 35%.
Test example:
the aqueous metallic flashing paints for automobiles of 8 groups were prepared according to the formulation of table 1, wherein the aqueous polyurethane-polyacrylate resins in the aqueous metallic flashing paints for automobiles of 1 st to 6 th groups were respectively the aqueous polyurethane-polyacrylate resins prepared in examples 1 to 6, and the aqueous polyurethane-polyacrylate resins in the aqueous metallic flashing paints for automobiles of 7 th to 8 th groups were respectively the aqueous polyurethane-polyacrylate resins prepared in comparative examples 1 and 2, and the properties of the finally prepared aqueous metallic flashing paints for automobiles were respectively tested, and the test results are shown in table 2.
TABLE 1 formulation of water-based metallic flashing paint for automobiles
| Raw material | w/% |
| Aqueous polyurethane-polyacrylate resin | 65 |
| Hydrolan2153 aluminium powder ECKART | 15 |
| BYK-190 dispersant | 0.3 |
| SURFYNOL 440 wetting agent EVONIK | 0.5 |
| Dipropylene glycol dimethyl ether | 7.1 |
| Deionized water | 12 |
| pH regulator AMP-95 | 0.1 |
TABLE 2 Performance test results of water-based metallic flashing paint for automobiles
| Detection of Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Detection method Method of making |
| Appearance of the product | Leveling and flattening | Leveling and flattening | Leveling and flattening | Leveling and flattening | Leveling and flattening | Leveling and flattening | Leveling and flattening | Flattening and leveling | Eye test |
| Adhesion force (grade) | 1 | 1 | 0 | 0 | 1 | 1 | 4 | 4 | GB/T 9286- 98 |
| Flexibility （1mm） | No reticulate pattern, no Crack and no peeling Fall to | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | No reticulate pattern, no Crack and no peeling Fall off | GB/T 1731- 93 |
| Water resistance （240h） | Qualified | Qualified | Qualified | Whitening of the skin | Qualified | Qualified | Whitening of rice | Qualified | GB/T 1733- 93 |
| Acid resistance （24h） | Qualified | Qualified | Qualified | Whitening of the skin | Qualified | Qualified | Qualified | Qualified | GB/T 9274- 1988 |
| Alkali resistance （24h） | Qualified | Qualified | Qualified | Whitening of the skin | Qualified | Qualified | Qualified | Qualified | GB/T 9274- 1988 |
| Gasoline resistant Property of (2) （24h） | Qualified | Qualified | Qualified | Whitening of the skin | Qualified | Qualified | Qualified | Whitening of the skin | GB/T 1734- 1993 |
| Anti-stone-strike (grade) | 2 | 2 | 1 | 1 | 2 | 2 | 4 | 4 | ISO 20567 |
As can be seen from Table 2, the paint film of the waterborne metallic flashing paint for the automobile, which is prepared from the waterborne polyurethane-polyacrylate resin, has excellent stone impact resistance, the stone impact resistance level can reach 2 levels or above, and the paint film has excellent flexibility; when the aqueous polyurethane-polyacrylate resin is prepared in the step (2), the weight ratio of the aqueous polyurethane prepolymer to the acrylic acid monomer is (10-40): (3-16), when the prepared waterborne polyurethane-polyacrylate resin is applied to the waterborne metallic flashing paint for the automobile, the paint film has better water resistance, acid resistance, alkali resistance and gasoline resistance; when the waterborne polyurethane prepolymer is prepared in the step (1), the used functional monomer comprises tertiary carbonic acid glycidyl ester, and the weight ratio of the functional monomer to the hydrophilic monomer is (1-4): (1-5), when the prepared waterborne polyurethane-polyacrylate resin is applied to the waterborne metallic flashing paint for the automobile, a paint film has better adhesive force and stone chip resistance, the adhesive force can reach 0 level, and the stone chip resistance can reach 1 level.
Further, by comparing example 3 with comparative example 1 and example 3 with comparative example 2, respectively, it can be seen that when the aqueous polyurethane prepolymer used in the step (2) does not contain functional monomers or hydrophilic monomers, the adhesion and stone-chip resistance are greatly reduced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 403 parts of (1);
t-butyl hydroperoxide: 3 parts of a mixture;
methyl methacrylate: 12 parts of (a);
divinylbenzene: 2 parts of (1);
ethyl acrylate: 10 parts of (A);
butyl methacrylate: 15 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polyester diol: 30 parts of a binder;
hexamethylene diisocyanate: 15 parts of (1);
isophorone diisocyanate: 15 parts of a mixture;
methyl isobutyl ketone: 15 parts of (1);
dimethylolbutyric acid: 8 parts of a mixture;
glycerol: 3 parts of a mixture;
linoleic acid: 3 parts of a mixture;
organic bismuth: 2 parts of (1);
1.6-hexanediol: 8 parts;
acrylamide: 3 parts of a mixture;
styrene: 26 parts of (1);
lauryl acrylate: 10 parts of a binder;
glycidyl methacrylate: 6 parts;
methacrylic acid: 5 parts of a mixture;
triethylamine: 6 parts of (1);
deionized water: 248 parts of (a);
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparing a waterborne polyurethane prepolymer: under the protection of nitrogen, adding 30 parts of saturated polyester diol, 15 parts of hexamethylene diisocyanate, 15 parts of isophorone diisocyanate and 15 parts of methyl isobutyl ketone into a reactor, slowly raising the temperature to 85 ℃, and reacting for 2 hours; adding 8 parts of dimethylolbutyric acid, 3 parts of glycerol, 3 parts of linoleic acid and 2 parts of organic bismuth, further reacting for 2 hours at the temperature of 90 ℃, adding 8 parts of 1.6-hexanediol for chain extension reaction, stirring for reaction for 1 hour, cooling, adding an acrylic acid mixed solution into a reaction kettle, stirring for 1 hour, adding 6 parts of triethylamine for neutralization reaction, adding 248 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare a waterborne polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) comprises the following raw materials in parts by weight: 3 parts of acrylamide, 26 parts of styrene, 10 parts of lauryl acrylate, 6 parts of glycidyl methacrylate and 5 parts of methacrylic acid;
(2) Preparing the waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 80 ℃, dissolving 3 parts of tert-butyl hydroperoxide in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving heat for 3 hours after dropwise adding is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 15 mg KOH/g, the viscosity is 85mPa.s, the vitrification temperature is 30 ℃, the solid content is 40%, and the acrylic acid mixed solution in the step (2) is composed of the following raw materials in parts by weight: 12 parts of methyl methacrylate, 2 parts of divinylbenzene, 10 parts of ethyl acrylate and 15 parts of butyl methacrylate.
2. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 351 parts of a stabilizer;
lauroyl peroxide: 3 parts of a mixture;
butyl methacrylate: 16 parts of a binder;
diacetone acrylamide: 3 parts of a mixture;
ethyl acrylate: 10 parts of (A);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
unsaturated polycarbonate diol: 32 parts of (1);
cyclohexane dimethylene diisocyanate: 25 parts of a binder;
hexamethylene diisocyanate trimer: 2 parts of (1);
butanone: 15 parts of (1);
polyethylene glycol: 15 parts of a mixture;
trimethylolpropane monoallyl ether: 8 parts of a mixture;
soybean oleic acid: 2 parts of (1);
tin dilaurate: 2 parts of (1);
hexamethylene diamine: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
n-butyl acrylate: 18 parts of a mixture;
styrene: 12 parts of (a);
t-butyl acrylate: 6 parts of (1);
dimethylethanolamine: 4 parts;
deionized water: 200 parts of (A);
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 32 parts of unsaturated polycarbonate dihydric alcohol, 25 parts of cyclohexane dimethylene diisocyanate, 2 parts of hexamethylene diisocyanate tripolymer and 15 parts of butanone into a reactor, slowly raising the temperature to 105 ℃, and reacting for 2 hours; adding 15 parts of polyethylene glycol, 8 parts of trimethylolpropane monoallyl ether, 2 parts of soybean oleic acid and 2 parts of tin dilaurate, further reacting for 3 hours at 95 ℃, adding 5 parts of hexamethylenediamine for chain extension reaction, stirring for reaction for 3 hours, cooling, adding the acrylic acid mixed solution into a reaction kettle, stirring for 2 hours, adding 4 parts of N, N' -dimethylethanolamine for neutralization reaction, adding 200 parts of deionized water under a high shear condition, and stirring for 1 hour to prepare the waterborne polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) is prepared from the following raw materials in parts by weight: 5 parts of lauryl acrylate, 18 parts of n-butyl acrylate, 12 parts of styrene and 6 parts of tert-butyl acrylate;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 80 ℃, dissolving 3 parts of lauroyl peroxide in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving heat for 3 hours after the dropwise adding is finished, cooling after the reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 36 mg KOH/g, the viscosity is 700mPa.s, the vitrification temperature is 35 ℃, the solid content is 35%, and the acrylic acid mixed solution in the step (2) is prepared from the following raw materials in parts by weight: 16 parts of butyl methacrylate, 3 parts of diacetone acrylamide and 10 parts of ethyl acrylate.
3. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of a binder;
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of a mixture;
butyl acetate: 13 parts of (1);
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
glycidyl versatate: 3 parts of a mixture;
pentaerythritol: 2 parts of (1);
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of a mixture;
butyl methacrylate: 10 parts of (A);
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 parts of (A);
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1.4-butanediol-2-sodium sulfonate, 3 parts of glycidyl versatate, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1.4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution into a reaction kettle, stirring for 2 hours, adding 2 parts of N, N' -diisopropylethylamine, adding 230 parts of deionized water under a high shearing condition, and stirring for 2 hours to prepare an aqueous polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) comprises the following raw materials in parts by weight: 15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 90 ℃, dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving heat for 4 hours after dropwise adding is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 33 mg KOH/g, the viscosity is 750mPa.s, the vitrification temperature is 36 ℃, the solid content is 35%, and the acrylic acid mixed solution in the step (2) is composed of the following raw materials in parts by weight: 5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate.
4. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 464.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of a binder;
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of (1);
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of a binder;
glycidyl versatate: 3 parts of a mixture;
pentaerythritol: 2 parts of (1);
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of a binder;
methyl methacrylate: 15 parts of a mixture;
butyl methacrylate: 10 parts of a binder;
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 330 parts of (B);
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1.4-butanediol-2-sodium sulfonate, 3 parts of glycidyl versatate, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1.4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution into a reaction kettle, stirring for 2 hours, adding 2 parts of N, N' -diisopropylethylamine, adding 330 parts of deionized water under a high shear condition, and stirring for 2 hours to prepare an aqueous polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) comprises the following raw materials in parts by weight: 15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 90 ℃, dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving the temperature for 4 hours after the dropwise adding is finished, cooling after the reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 28 mg KOH/g, the viscosity is 600mPa.s, the vitrification temperature is 36 ℃, the solid content is 35%, and the acrylic acid mixed solution in the step (2) is composed of the following raw materials in parts by weight: 5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate.
5. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of a binder;
tetramethylxylylene diisocyanate: 15 parts of a mixture;
diphenylmethane diisocyanate: 15 parts of a mixture;
butyl acetate: 13 parts;
1.4-butanediol-2-sulfonic acid sodium salt: 13 parts;
glycidyl versatate: 1 part;
pentaerythritol: 1 part;
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of (A);
methyl methacrylate: 15 parts of a mixture;
butyl methacrylate: 10 parts of (A);
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of a mixture;
deionized water: 230 parts of;
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 13 parts of 1.4-butanediol-2-sodium sulfonate, 1 part of glycidyl versatate, 1 part of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, adding 10 parts of 1.4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution into a reaction kettle, stirring for 2 hours, adding 2 parts of N, N' -diisopropylethylamine, adding 230 parts of deionized water under a high shearing condition, and stirring for 2 hours to prepare an aqueous polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) comprises the following raw materials in parts by weight: 15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 90 ℃, dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving heat for 4 hours after dropwise adding is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 35 mg KOH/g, the viscosity is 760mPa.s, the vitrification temperature is 36 ℃, the solid content is 35%, and the acrylic acid mixed solution in the step (2) is composed of the following raw materials in parts by weight: 5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate.
6. The waterborne polyurethane-polyacrylate resin is characterized by comprising the following raw materials in parts by weight:
aqueous polyurethane prepolymer: 364.5 parts;
azobisisobutyronitrile: 5 parts of a mixture;
lauryl acrylate: 5 parts of a mixture;
ethyl acrylate: 3 parts of a mixture;
methyl methacrylate: 20 parts of (1);
the waterborne polyurethane prepolymer comprises the following raw materials in parts by weight:
saturated polycarbonate diol: 28 parts of (1);
tetramethylxylylene diisocyanate: 15 parts of (1);
diphenylmethane diisocyanate: 15 parts of a mixture;
butyl acetate: 13 parts of (1);
1.4-butanediol-2-sulfonic acid sodium salt: 10 parts of (A);
trimethylolpropane monoallyl ether: 3 parts of a mixture;
pentaerythritol: 2 parts of a mixture;
dibutyl tin acetate: 3.5 parts;
1.4-butanediol: 10 parts of a binder;
methyl methacrylate: 15 parts of (1);
butyl methacrylate: 10 parts of a binder;
cyclohexyl acrylate: 5 parts of a mixture;
2-hydroxyethyl acrylate: 3 parts of a mixture;
n, N' -diisopropylethylamine: 2 parts of (1);
deionized water: 230 parts of;
the preparation method of the waterborne polyurethane-polyacrylate resin comprises the following steps:
(1) Preparation of waterborne polyurethane prepolymer: under the protection of nitrogen, adding 28 parts of saturated polycarbonate diol, 15 parts of tetramethylxylylene diisocyanate, 15 parts of diphenylmethane diisocyanate and 13 parts of butyl acetate into a reactor, slowly raising the temperature to 100 ℃, and reacting for 1 hour; adding 10 parts of 1, 4-butanediol-2-sodium sulfonate, 3 parts of trimethylolpropane monoallyl ether, 2 parts of pentaerythritol and 3.5 parts of dibutyltin acetate, further reacting for 4 hours at 95 ℃, then adding 10 parts of 1, 4-butanediol for chain extension reaction, stirring for reacting for 2 hours, cooling, adding an acrylic acid mixed solution into a reaction kettle, stirring for 2 hours, then adding 2 parts of N, N' -diisopropylethylamine, adding 230 parts of deionized water under a high-shear condition, and stirring for 2 hours to prepare an aqueous polyurethane prepolymer, wherein the acrylic acid mixed solution in the step (1) comprises the following raw materials in parts by weight: 15 parts of methyl methacrylate, 10 parts of butyl methacrylate, 5 parts of cyclohexyl acrylate and 3 parts of acrylic acid-2-hydroxyethyl ester;
(2) Preparation of waterborne polyurethane-polyacrylate resin: under the protection of nitrogen, heating the aqueous polyurethane prepolymer prepared in the step (1) to 90 ℃, dissolving 5 parts of azodiisobutyronitrile in an acrylic acid mixed solution, slowly dropwise adding the mixed solution for 3 hours under the stirring condition, continuously preserving heat for 4 hours after dropwise adding is finished, cooling after reaction is finished, removing the solvent from the obtained resin in a reduced pressure suction filtration mode to obtain the aqueous polyurethane-polyacrylate resin, wherein the acid value of the aqueous polyurethane-polyacrylate resin is 36 mg KOH/g, the viscosity is 730mPa.s, the vitrification temperature is 36 ℃, the solid content is 35%, and the acrylic acid mixed solution in the step (2) is composed of the following raw materials in parts by weight: 5 parts of lauryl acrylate, 3 parts of ethyl acrylate and 20 parts of methyl methacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010932433.6A CN112175147B (en) | 2020-09-08 | 2020-09-08 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010932433.6A CN112175147B (en) | 2020-09-08 | 2020-09-08 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112175147A CN112175147A (en) | 2021-01-05 |
| CN112175147B true CN112175147B (en) | 2022-12-27 |
Family
ID=73925748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010932433.6A Active CN112175147B (en) | 2020-09-08 | 2020-09-08 | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112175147B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980256A (en) * | 2021-11-30 | 2022-01-28 | 珠海展辰新材料股份有限公司 | Water-based alkyd resin and preparation method thereof |
| CN116716075B (en) * | 2023-06-08 | 2023-12-08 | 广东中粘新材料科技有限公司 | Solvent-free environment-friendly modified polyurethane adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN104892849A (en) * | 2014-03-03 | 2015-09-09 | 广东多正化工科技有限公司 | Bionically designed waterborne polyacrylate modified polyurethane composite emulsion and preparation method thereof |
| CN109162123A (en) * | 2018-09-03 | 2019-01-08 | 武汉纺织大学 | Anionic polyurethane modified polyacrylate emulsion and preparation method thereof with cross-linked core-shell structure |
| CN110713705A (en) * | 2019-10-17 | 2020-01-21 | 广东工业大学 | Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof |
-
2020
- 2020-09-08 CN CN202010932433.6A patent/CN112175147B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN104892849A (en) * | 2014-03-03 | 2015-09-09 | 广东多正化工科技有限公司 | Bionically designed waterborne polyacrylate modified polyurethane composite emulsion and preparation method thereof |
| CN109162123A (en) * | 2018-09-03 | 2019-01-08 | 武汉纺织大学 | Anionic polyurethane modified polyacrylate emulsion and preparation method thereof with cross-linked core-shell structure |
| CN110713705A (en) * | 2019-10-17 | 2020-01-21 | 广东工业大学 | Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112175147A (en) | 2021-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100686674B1 (en) | Strippable Coating Compositions | |
| US5614582A (en) | Resinous compositions for a water paint | |
| US7521506B2 (en) | Emulsifier-free microgel | |
| CN105008472B (en) | Methods for repairing defects in automotive coatings | |
| CN112175147B (en) | Waterborne polyurethane-polyacrylate resin and preparation method and application thereof | |
| KR20130099070A (en) | Aqueous polyurethane resin dispersion, manufacturing method therefor, and use therefor | |
| US20110020556A1 (en) | Aqueous coating composition comprising polyurethanes and vinyl polymers | |
| CN102234369A (en) | Polyester resin and purposes thereof | |
| CN106794486B (en) | Method and composition for coating a substrate | |
| JP2003534437A (en) | Water-based crosslinkable binder composition and coating, lacquer or sealing composition containing the binder composition | |
| CN101622290A (en) | Radiation curable aqueous composition for low gloss coatings | |
| CN104254553A (en) | Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation | |
| KR20140048281A (en) | Aqueous polyurethane resin dispersion and use thereof | |
| CN101294045B (en) | Method for producing watersoluble floating coat paint suitable for original factory of vehicle and repair | |
| CN104995224A (en) | Aqueous resin dispersion and use of same | |
| JP2006056973A (en) | Method for producing aqueous resin dispersion | |
| CN111978506A (en) | Preparation method of aqueous hyperbranched polyurethane acrylate emulsion, UV (ultraviolet) curing coating and preparation method and application thereof | |
| US6998439B2 (en) | Resin composition, sheet obtained therefrom, process for producing sheet, and formed object | |
| CN107033320A (en) | Hydroxyl water-borne dispersions and preparation method thereof | |
| CN111909354B (en) | Waterborne polyurethane resin and preparation method and application thereof | |
| CN115595036A (en) | Acrylic acid modified polyurethane dispersion for plastic-replacing gloss oil and preparation method thereof | |
| KR101638794B1 (en) | Biomass-polymer polyurethane resin and method of manufacturing using the same | |
| JP2002302524A (en) | Method for producing polyurethane resin aqueous dispersion | |
| CN114316150B (en) | Water-based acrylic emulsion and preparation method and application thereof | |
| CN115141346B (en) | Detachable waterborne polyurethane dispersion for temporary bonding and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |