CN112175162B - Modified waterborne polyurethane resin, preparation method and application thereof - Google Patents
Modified waterborne polyurethane resin, preparation method and application thereof Download PDFInfo
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- CN112175162B CN112175162B CN201910601805.4A CN201910601805A CN112175162B CN 112175162 B CN112175162 B CN 112175162B CN 201910601805 A CN201910601805 A CN 201910601805A CN 112175162 B CN112175162 B CN 112175162B
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
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- 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
- C09D175/08—Polyurethanes from polyethers
Abstract
The invention provides a modified waterborne polyurethane resin, a preparation method and application thereof, wherein the resin is prepared by the reaction of isocyanate-terminated prepolymer and modified monomer, the preparation method comprises the following steps of synthesizing the isocyanate-terminated prepolymer, fully mixing and dissolving the monomer with the modification function and the isocyanate-terminated prepolymer, dispersing under high-speed shearing after neutralization reaction to obtain pre-modified emulsion, and adding an initiator into the pre-modified emulsion for initiating polymerization; the polyurethane resin can be used in the field of coatings, particularly wood lacquer, the preparation process of the modified waterborne polyurethane resin prepared by the preparation method is simple and controllable, the solid content of the synthesized resin is high, the particle size is small, and the application performance requirement in the field of wood lacquer is met.
Description
Technical Field
The invention belongs to the field of wood paint coatings, and particularly relates to a modified waterborne polyurethane resin, and a preparation method and application thereof.
Background
In recent years, under the increasingly strict environmental protection law of various countries, the market share of the water-based wood paint is increased year by year, the use rate of the water-based wood paint in Germany reaches 70%, the use rate in America reaches 80%, and the annual output is increased by 9%. However, the application performance of the wood lacquer coating is still to be improved, compared with a solvent type, the wood lacquer coating has low hardness, poor adhesion with a primer, poor effect of using the sealing primer alone, poor fullness, poor early-stage anti-sticking property, poor anti-contamination capability and the like, and the price is over high. Therefore, a wood lacquer resin with high hardness, low cost, good adhesion, resistance to pressure marks, adhesion resistance, high fullness and low dosage of film forming agent needs to be developed to meet the application requirement in the field of wood lacquer coatings.
Chinese patent application CN108623751A discloses a preparation method of acrylate modified waterborne polyurethane for waterborne wood lacquer, which takes sulfonate as a hydrophilic center, the sulfonate is a strong acid and strong alkali salt, the ionization degree is high, and strong hydrophilicity can be provided with a small amount of sulfonate.
Chinese patent application CN106279620A discloses a modified waterborne polyurethane resin for wood lacquer and a preparation method thereof, wherein a wood lacquer resin with high drying speed of a coating film, glossiness of more than 90 degrees, high pencil hardness and excellent water resistance is described, but as castor oil in a formula system has the characteristic of being dissolved in ethanol, the resin has poor chemical resistance and alcohol resistance and cannot meet the requirement of the high-end wood lacquer field on the chemical resistance. The modified waterborne polyurethane and the modified monomer acrylate thereof have the advantages of superior performance and price, and are widely applied to the field of wood lacquer coatings, but the performance requirements of wood lacquer use cannot be well met due to the characteristics of low fullness, poor compression mark resistance, poor film forming property and the like of the pure acrylic resin. The traditional waterborne polyurethane resin has low hardness, low drying speed and poor resistance, and can not meet the performance requirements of the wood lacquer.
Therefore, how to develop a wood lacquer resin with high hardness, good resistance, resistance to indentation, high fullness, high adhesion and low VOC has become one of the technical difficulties to be solved in the field.
Disclosure of Invention
The modified waterborne polyurethane resin prepared by the preparation method provided by the invention is simple and controllable in preparation process, and the synthesized resin has excellent performance, can be applied to the field of coatings, and meets the application performance requirement in the field of wood lacquer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a modified waterborne polyurethane resin which is prepared by the reaction of isocyanate-terminated prepolymer and modified monomer,
wherein the modified monomer comprises at least three of acrylate monomer, styrene monomer, tetrahydrofuran acrylate and 3-amino-4, 4, 4-ethyl trifluorocrotonate.
Preferably, the modifying monomer comprises tetrahydrofuran acrylate.
Preferably, the modified monomer contains 3-amino-4, 4, 4-trifluoro-ethyl crotonate.
In the present invention, the acrylate monomer includes, but is not limited to, one or more of methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, isobornyl acrylate, and isooctyl acrylate, preferably methyl methacrylate;
the styrene monomer comprises one or two of styrene and methyl styrene, and styrene is preferred.
The invention also provides a preparation method of the modified waterborne polyurethane resin, which comprises the following steps:
mixing and dissolving a modified monomer and an isocyanate-terminated prepolymer, carrying out high-speed shearing dispersion after neutralization reaction to obtain a pre-modified emulsion, and adding an initiator into the pre-modified emulsion to initiate polymerization;
the isocyanate-terminated prepolymer is prepared by mixing and reacting the following raw materials: diisocyanate, macromolecular polyol and a chain extender; the macromolecular polyol comprises at least one of polyether diol and polyester diol. A catalyst can also be added in the preparation process of the isocyanate-terminated prepolymer, and the catalyst comprises an organic tin catalyst, an organic zinc catalyst and an organic bismuth catalyst, preferably an organic bismuth catalyst.
The production method of the present invention is, preferably, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin, the following raw materials for producing the isocyanate terminated prepolymer: the mass fraction of diisocyanate is 20 to 50 wt.%, preferably 30 to 45 wt.%; the mass fraction of the chain extender is 5-15wt%, preferably 8-12 wt%;
in the present invention, the molar ratio of the macromolecular polyol to the diisocyanate in the production of the isocyanate terminated prepolymer is 1:2.5 to 1:7, and more preferably 1:4.5 to 1:6.5, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin.
In the preparation method of the invention, preferably, the number average molecular weight of the polyether diol or the polyester diol is 500-3000, more preferably 1000-2000, and even more preferably 2000, which is beneficial to improving the fullness and the indentation resistance of a coating film formed by the resin prepared into the wood lacquer coating, so as to obtain a better use effect.
In the preparation method of the present invention, preferably, the chain extender includes a small molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender. Preferably, the small molecule polyol chain extender is used in an amount of 1 to 5wt%, preferably 2 to 4wt%, and the carboxylic acid type hydrophilic chain extender is used in an amount of 5 to 10wt%, preferably 6 to 9wt%, based on the total mass of the prepolymer for preparing the modified aqueous polyurethane resin. Preferably, the small-molecule polyol chain extender is a polyol chain extender containing active hydrogen, and the molecular weight of the polyol chain extender is preferably 30-200 g/mol. Preferably, the carboxylic acid type hydrophilic chain extender is a carboxylic acid type hydrophilic chain extender containing active hydrogen.
In the preparation method of the present invention, preferably, the total amount of the modified monomer is 0.9 to 1.6 times, preferably 1.0 to 1.4 times the amount of the isocyanate terminated prepolymer. Preferably, the amount of the acrylate monomer is 0.6 to 0.9 times the amount of the isocyanate terminated prepolymer, preferably methyl methacrylate, the amount of the styrene monomer is 0.18 to 0.36 times the amount of the isocyanate terminated prepolymer, preferably styrene, the amount of the tetrahydrofuran acrylate is 0.05 to 0.1 times the amount of the isocyanate terminated prepolymer, and the amount of the ethyl 3-amino-4, 4, 4-trifluorocrotonate is 0.1 to 0.2 times the amount of the isocyanate terminated prepolymer. Preferably, the isocyanate-terminated prepolymer is diluted and dissolved with a solvent, which is an organic solvent having a boiling point of less than 100 ℃, such as acetone, butanone or the like, preferably acetone is used, at the time of preparing the isocyanate prepolymer and at the time of adding the modifying monomer. The total amount of the solvent added is preferably 0.8 to 1.2 times the amount of the isocyanate terminated prepolymer.
In the preparation method of the invention, preferably, the amount of the initiator is 0.05-0.3% of the mass of the modified monomer, and preferably 0.1-0.2%; preferably, the initiator comprises an oxidizing agent and a reducing agent; further preferably, the oxidizing agent comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate and tert-butyl hydroperoxide, and further preferably, the reducing agent comprises one or more of sodium hydrosulfite, sodium hydrogen sulfite and isoascorbic acid. A more preferred initiator is a combination of both t-butyl hydroperoxide and sodium hydrosulfite.
In a more preferred embodiment of the preparation method of the present invention, based on the total mass of the prepolymer for preparing the modified aqueous polyurethane resin, the isocyanate-terminated prepolymer is prepared by mixing and reacting the following components in percentage by mass: 20-50wt% of diisocyanate, 1-5wt% of micromolecular polyol chain extender and 5-10wt% of carboxylic acid type hydrophilic chain extender; also contains macromolecular polyol, wherein the molar ratio of the macromolecular polyol to diisocyanate is 1:2.5-1: 7; based on the total mass of the prepolymer for preparing the modified waterborne polyurethane resin, the using amount of the modified monomer is 0.9-1.6 times of the mass of the isocyanate-terminated prepolymer; the using amount of the initiator is 0.05-0.3% of the mass of the modified monomer.
In a more preferred embodiment of the preparation method of the present invention, based on the total mass of the prepolymer for preparing the modified aqueous polyurethane resin, the isocyanate-terminated prepolymer is prepared by mixing and reacting the following components in percentage by mass: 30-45wt% of diisocyanate, 2-3 wt% of micromolecular polyol chain extender and 6-9wt% of carboxylic acid type hydrophilic chain extender; also contains macromolecular polyol, wherein the molar ratio of the macromolecular polyol to the diisocyanate is 1:4.5-1: 6.5; based on the total mass of the prepolymer for preparing the modified waterborne polyurethane resin, the using amount of the modified monomer is 1.0-1.4 times of the mass of the isocyanate-terminated prepolymer; the using amount of the initiator is 0.1-0.2% of the mass of the modified monomer.
In a preferred embodiment of the preparation method of the present invention, the diisocyanate includes, but is not limited to, one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
In a preferred embodiment of the preparation method of the present invention, the macropolyol includes, but is not limited to, one or more of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polycarbonate glycol, polyethylene adipate glycol, 1, 4-butanediol adipate glycol, neopentyl glycol adipate glycol, 1, 6-hexanediol adipate glycol and 1, 6-hexanediol adipate glycol, more preferably polytetrahydrofuran ether glycol, further preferably polytetrahydrofuran ether glycol having a number average molecular weight of 1000-.
In a preferred embodiment of the preparation method of the present invention, the chain extender includes a small molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender; the chain extender of the small molecular weight polyol preferably contains active hydrogen and more than two active groups capable of reacting with isocyanate, preferably comprises but is not limited to one or two of trimethylolpropane and 1, 4-butanediol, and more preferably is trimethylolpropane; the carboxylic acid type hydrophilic chain extender preferably includes, but is not limited to, a small molecule diol compound having a carboxylate group, preferably including one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, N-dimethylolmaleamic acid, more preferably dimethylolpropionic acid.
In the preparation method of the invention, in a preferred embodiment, the reaction temperature used for preparing the hydroxyl-terminated prepolymer is 75-85 ℃; the end point of the reaction can be determined in particular by reacting until the NCO has reached the theoretical value.
In the production method of the present invention, in a preferred embodiment, the mixing and dissolving of the modifying monomer and the isocyanate terminated prepolymer is carried out at 50 to 60 ℃.
In the preparation method of the invention, the initiation temperature of the pre-modified emulsion initiation polymerization is 30-35 ℃. In one embodiment, the polymerization time is preferably 1 to 2 hours.
As a specific embodiment, the neutralization reaction is performed by adding a neutralizing agent to a mixed solution obtained by mixing and dissolving a modified monomer and an isocyanate-terminated prepolymer, which is a conventional operation in the field and is not described in detail. The neutralizing agent added for the neutralization reaction is Triethylamine (TEA) or the like, and is preferably 100% neutralized.
The preparation method of the present invention, in a preferred embodiment, further comprises the following steps after initiating polymerization: the solvent in the modified aqueous polyurethane resin obtained by the initiation of polymerization may be removed by, for example, distillation under reduced pressure.
The invention also provides the application of the modified waterborne polyurethane resin and the modified waterborne polyurethane resin prepared by the preparation method, which is suitable for preparing coatings, in particular for preparing wood paint coatings, and is preferably used for preparing wood paint coatings suitable for American coating, toys or furniture surfaces. The wood lacquer coating comprises the modified waterborne polyurethane resin.
As used herein, "plurality" means two and more than two.
The technical scheme provided by the invention has the following beneficial effects:
according to the invention, a modified monomer 3-amino-4, 4, 4-ethyl trifluorocrotonate is introduced, active hydrogen provided by primary amine can react with isocyanate, and unsaturated double bonds can participate in polymerization of a PA monomer section, so that grafting of a PU section and the PA section is increased for the PUA with an original core-shell structure, and the application performance is obviously improved; in addition, the monomer contains fluorine units, and the long bond and the short bond of the C-F bond are high in energy, so that the polymer is endowed with a plurality of special properties, such as: the coating has the advantages that the coating has high thermal stability, chemical resistance, weather resistance, low surface energy and the like, the fluorine surface energy is low, the film forming process migrates to the surface of the coating, and the paint film meets the performance requirements of scratch resistance, chemical resistance, indentation resistance and the like of the wood lacquer; the tetrahydrofuran acrylate is a functional monomer with low viscosity and high polarity and containing a cyclic functional group, the high polarity enables the tetrahydrofuran acrylate to have strong dilutability, the low Tg enables the tetrahydrofuran acrylate to have good flexibility and film forming, the tetrahydrofuran acrylate has excellent adhesion effect on most substrates, the cyclic structure of the tetrahydrofuran acrylate has obvious effect on the critical anti-indentation performance in wood lacquer application, and the tetrahydrofuran acrylate has obvious effect on the water resistance and the chemical resistance in the wood lacquer resistance.
Compared with the traditional aqueous acrylic resin and acrylate modified aqueous polyurethane resin, the resin prepared by the invention meets the performance requirements of wood lacquer application, has obvious performance advantages by introducing a special functional monomer, overcomes the defect that the common aqueous wood lacquer can not be used as a sealing primer independently, has high hardness, good toughness, low VOC content, high drying speed and high construction efficiency, meets the requirement of resisting the indentation problem in the construction process, and has good thickness and high fullness.
The resin prepared by the preparation method can be used as a 2K system in the application process, and the resin has good dispersibility, long opening time and better performance by adding the curing agent, and meets the application requirements of the 2K system.
Compared with the traditional waterborne polyurethane/acrylic wood resin, the resin provided by the invention has a good adhesion effect with a UV primer, solves the problem of poor adhesion in the industry at present, and can form a coating film with strength, hardness and resistance meeting the use requirements.
Compared with the existing aqueous wood resin, the resin disclosed by the invention has high extinction efficiency, and the application cost cannot be increased.
The average particle size of the resin prepared by the invention is in the range of 50-120nm, and preferably in the range of 60-90 nm.
The modified waterborne polyurethane resin provided by the invention has the advantages of safe and controllable synthesis process, simple operation and easy realization of large-scale industrial production.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the examples and comparative examples, "%" means "% by weight" unless otherwise specified.
The test methods used in the examples or comparative examples are described below:
the solid content test method comprises the following steps: weighing appropriate amount of the emulsion in a container made of tinfoil paper, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
pH test method: a pH meter was used.
Viscosity test method: the measurements were carried out using a BROOKFIELD viscometer, spindle 3/30 rpm.
The appearance test method comprises the following steps: and judging the eye sight.
The following examples or comparative examples produce emulsions having the following formulations for use in preparing coatings in Table 1 below:
TABLE 1
| Name (R) | Material(s) | Mass/g |
| Emulsions from the examples or comparative examples | Emulsion and method of making | 80 |
| Tego 825 | Defoaming agent | 0.2 |
| Tego 902W | Defoaming agent | 0.1 |
| Tego 245 | Wetting agent | 0.3 |
| Tego 270 | Wetting agent | 0.3 |
| DPM | Film forming aid | 3 |
| DPnB | Film forming aid | 5 |
| U605 | Thickening agent | 0.4 |
| Water (W) | Diluent | 10.7 |
The method for testing the application properties of the comparative examples after the examples is described as follows:
template construction process: substrate-waterborne bottom color correction-waterborne top primer-waterborne Glaze-waterborne transparent primer-waterborne surface color correction-waterborne clear finish.
The dry speed testing method comprises the following steps: with reference to GB/T1728-79(1989), the paint film surface is touched with a finger, but no paint sticks to the finger, i.e. the surface is considered dry.
Coating film appearance test method: referring to GB/T9756-2009, the sprayed sample plate is placed for 24h, the coating film is visually observed, and if no obvious shrinkage cavity exists and the coating film is uniform, the sample plate is evaluated to be normal.
Pencil hardness test method: a set of pencils with hardness of 6B, 5B, 4B, 3B, 2B, HB, F, H, 2H, 3H, 4H and 5H are adopted, 1000 gram force is applied to the coating film in a 45-degree direction, a stroke of 10 millimeters is marked at different positions, whether obvious scratches exist in the appearance of the sample is observed, and the hardness of the pencil with the hardest pencil number which cannot scratch the coating film is taken as the hardness of the pencil of the coating film.
Indentation resistance test method: and (3) coating a 120-micron waterborne clear finish on a wet film on a glass plate, immediately putting the sample plate into a constant-temperature constant-humidity drying box with the temperature of 25 ℃ and the humidity of 80% after finishing coating, drying for 4 hours, covering a layer of medical gauze on the surface of the paint film, pressing weights with different PSI (pressure specific integrated circuits), taking down the weights and the gauze after pressing for 16 hours, observing whether indentation marks exist on the surface of the paint film, and taking the highest PSI (pressure specific integrated circuit) without marks on the surface of the paint film as the PSI value for the anti-indentation property of the paint film to pass.
Chemical resistance test method: placing test item quantity of cotton white paper sheets on the fully dried sample plate after the preparation process is completed, wetting the paper sheets with 50% ethanol, 10% acetic acid and 10% sodium carbonate solution respectively, and placing for 24 h. And (4) taking away the paper after the test is finished, and observing residual marks on the sample plate, wherein the mark-free condition is the optimal condition.
The starting materials used in the examples or comparative examples are described below:
PPG-2000 (polyoxypropylene ether glycol, hydroxyl number 56mgKOH/g, number average molecular weight 2000, functionality of 2, Vanhua chemical group, Inc.);
PTMEG-1000 (polytetrahydrofuran ether glycol, hydroxyl value 112mgKOH/g, number average molecular weight 1000, functionality 2, BASF, germany);
PTMEG-2000 (polytetrahydrofuran ether glycol, hydroxyl value 56mgKOH/g, number average molecular weight 2000, functionality 2, BASF, germany);
TMP (trimethylolpropane, BASF, germany);
DMPA (dimethylolpropionic acid, boston);
BDO (1, 4-butanediol, medium petrochemical)
8108 (organic bismuth catalyst, leading in the United states)
TEA (triethylamine, Zibo Min Poly chemical);
acetone (refined by Wanhua chemical group GmbH)
MMA (methyl methacrylate, zilu petrochemical);
st (styrene, winnowing);
THFA (tetrahydrofuran acrylate, Disman)
3-amino-4, 4, 4-trifluoro-butenoic acid ethyl ester (Shanghai Peng chemical)
AA (acrylic acid, Wanhua chemical group, Ltd.)
APS (ammonium persulfate, chemical industry Co., Ltd.)
NaHCO3(sodium bicarbonate, Shirong chemical Co., Ltd.)
Sodium hydrosulfite (sodium hydrosulfite, available from Xiong chemical Co., Ltd.)
TBHP (tert-butyl hydroperoxide, Shigaku chemical Co., Ltd.)
U605 (thickener, Wanhua chemical group Co., Ltd.)
Comparative example 1:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate), 100g PTMEG2000 (polytetrahydrofuran ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until NCO reaches a theoretical value, and stopping the reaction.
Cooling to below 60 ℃, adding 134g of acetone, cooling to below 40 ℃, adding 12.06g of triethylamine, and carrying out neutralization reaction for 5 min.
The prepared prepolymer is poured into a dispersion cup, 315g of deionized water is added under the high-speed shearing condition of 1500r/min to obtain aqueous polyurethane emulsion, and then 2.8g of ethylenediamine is added for chain extension reaction.
The acetone in the emulsion is removed by a reduced pressure distillation mode to obtain the waterborne polyurethane emulsion with 40 percent of solid content, 23nm of grain diameter and transparent appearance.
Comparative example 2:
a wide-mouth bottle was charged with 240g of distilled water, 16g of DS-4AP (22.5%) (sodium dodecylbenzenesulfonate), 200g of styrene, 404g of methyl methacrylate, and 9g of acrylic acid, and the pre-emulsion was prepared under high-speed (1000r/min) stirring.
4.2g of DS-4AP (22.5%) (sodium dodecylbenzenesulfonate), 3.6g of sodium bicarbonate and 600g of distilled water were put into a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel and mechanical stirring, and heated to 85 ℃ to add 36g of the prepared pre-emulsion and 2.5g of ammonium persulfate to initiate a reaction.
After 10 minutes, the pre-emulsion was slowly dropped into the flask using a dropping funnel, over 4 hours, and incubated for 1 hour. Then cooling to 70 ℃, adding 2.4g of tert-butyl hydroperoxide and 1.2g of sodium hydrosulfite, cooling to room temperature after 1 hour, and discharging to obtain acrylic emulsion with solid content of about 40% and particle size of 98 nm.
Comparative example 3:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate), 100g PPG2000 (polypropylene oxide ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until NCO reaches a theoretical value, and stopping the reaction.
The temperature is reduced to below 60 ℃, 134g of acetone, 42g of styrene and 168g of methyl methacrylate are added, mixed and dissolved.
The temperature is reduced to below 40 ℃, 12.06g of triethylamine is added, and neutralization reaction is carried out for 5 min.
And pouring the prepared prepolymer into a dispersion cup, adding 630g of water under the high-speed shearing condition of 1500r/min to obtain a water-based polyurethane-acrylate mixed emulsion, and then adding 2.8g of ethylenediamine for chain extension reaction.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.315g of t-butyl hydroperoxide and 0.315g of sodium dithionite in that order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 78nm is obtained.
Example 1:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 72g
HMDI (dicyclohexylmethane diisocyanate), 100g PTMEG1000 (polytetrahydrofuran ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 5.4g trimethylolpropane, 14.6g dimethylolpropionic acid, 1.2g1, 4-butanediol and 58g acetone, heating to 75 ℃ for reaction, and reacting every 1hThe NCO was measured by sampling until the NCO reached the theoretical value and the reaction was stopped.
Cooling to below 60 deg.C (50-60 deg.C), adding 130g acetone, 11.6g tetrahydrofuran acrylate, 23.2g 3-amino-4, 4, 4-trifluoro-ethyl crotonate, 46.4g styrene, and 150.8g methyl methacrylate, mixing and dissolving.
And cooling to below 40 ℃, adding 11g of triethylamine, and reacting for 5 min.
Pouring the prepared prepolymer into a dispersion cup, and adding 638g of water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate mixed emulsion. Then, 2.4g of ethylenediamine was added to conduct a chain extension reaction.
Transferring the emulsion into a four-neck flask equipped with a reflux condenser, a thermometer and a mechanical stirrer, heating to about 32 ℃, sequentially adding 0.348g of tert-butyl hydroperoxide and 0.348g of sodium hydrosulfite to initiate free radical polymerization,
after the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 78nm is obtained.
Example 2:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate), 100g PPG2000 (polypropylene oxide ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until NCO reaches a theoretical value, and stopping the reaction.
Cooling to below 60 deg.C (50-60 deg.C), adding 134g acetone, 12.5g tetrahydrofuran acrylate, 25g 3-amino-4, 4, 4-trifluoro-ethyl crotonate, 50.4g styrene, and 164.1g methyl methacrylate, mixing and dissolving.
The temperature is reduced to below 40 ℃, 12.06g of triethylamine is added, and neutralization reaction is carried out for 5 min.
Pouring the prepared prepolymer into a dispersion cup, adding 693g of water under the high-speed shearing condition of 1500r/min to obtain a water-based polyurethane-acrylate mixed emulsion, and then adding 2.8g of ethylenediamine for chain extension reaction.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.378g of t-butyl hydroperoxide and 0.378g of sodium dithionite in order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 85nm is obtained.
Example 3
To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate), 100g PTMEG2000 (polytetrahydrofuran ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until NCO reaches a theoretical value, and stopping the reaction.
The temperature is reduced to below 60 ℃ (between 50 and 60 ℃), 134g of acetone, 14.7g of tetrahydrofuran acrylate, 29.4g of 3-amino-4, 4, 4-trifluoro-butenoic acid ethyl ester, 58.8g of styrene and 186.1g of methyl methacrylate are added and mixed and dissolved.
The temperature is reduced to below 40 ℃, 12.06g of triethylamine is added, and neutralization reaction is carried out for 5 min.
Pouring the prepared prepolymer into a dispersion cup, adding 753g of water under the high-speed shearing condition of 1500r/min to obtain aqueous polyurethane-acrylate mixed emulsion, and then adding 2.8g of ethylenediamine for chain extension reaction.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.44g of t-butyl hydroperoxide and 0.44g of sodium dithionite in this order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 101nm is obtained.
Example 4
To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate), 100g PTMEG2000 (polytetrahydrofuran ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until NCO reaches a theoretical value, and stopping the reaction.
The temperature is reduced to below 60 ℃ (50-60 ℃), 134g acetone, 12.6g tetrahydrofuran acrylate, 25.2g 3-amino-4, 4, 4-trifluoro-ethyl crotonate, 50.4g styrene and 164.1g methyl methacrylate are added and mixed and dissolved.
The temperature is reduced to below 40 ℃, 12.06g of triethylamine is added, and neutralization reaction is carried out for 5 min.
Pouring the prepared prepolymer into a dispersion cup, adding 693g of water under the high-speed shearing condition of 1500r/min to obtain a water-based polyurethane-acrylate mixed emulsion, and then adding 2.8g of ethylenediamine for chain extension reaction.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.378g of t-butyl hydroperoxide and 0.378g of sodium dithionite in order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 83nm is obtained.
Example 5
To a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 86g
HMDI (dicyclohexylmethane diisocyanate)Ester), 100g PTMEG2000 (polytetrahydrofuran ether glycol), 0.06g8108 catalyst, heating to 80 ℃ for reaction for 1h, cooling to below 60 ℃, adding 6g trimethylolpropane, 16g dimethylolpropionic acid, 2g1, 4-butanediol and 60g acetone, heating to 75 ℃ for reaction, sampling every 1h, measuring NCO until NCO reaches a theoretical value, and stopping reaction.
Cooling to below 60 deg.C (50-60 deg.C), adding 134g acetone, 10.5g tetrahydrofuran acrylate, 21g 3-amino-4, 4, 4-trifluoro-ethyl crotonate, 42g styrene, and 136.5g methyl methacrylate, mixing and dissolving.
The temperature is reduced to below 40 ℃, 12.06g of triethylamine is added, and neutralization reaction is carried out for 5 min.
And pouring the prepared prepolymer into a dispersion cup, adding 630g of water under the high-speed shearing condition of 1500r/min to obtain a water-based polyurethane-acrylate mixed emulsion, and then adding 2.8g of ethylenediamine for chain extension reaction.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, heated to about 32 ℃ and then charged with 0.315g of t-butyl hydroperoxide and 0.315g of sodium dithionite in that order to initiate radical polymerization.
After the polymerization is finished, acetone in the emulsion is removed in a reduced pressure distillation mode, and the semitransparent blue-emitting modified waterborne polyurethane emulsion with the solid content of 40% and the particle size of 72nm is obtained.
The emulsions prepared in the examples and comparative examples were used to prepare wood lacquer coatings according to the coating formulations provided above and were tested for performance. The performance test results of the obtained wood lacquer coating are shown in the following table 1:
the embodiment shows that the resin prepared by the invention can meet the performance requirements in the field of wood lacquer, the most optimal scheme in the embodiment 4 has obvious effect comparison with the comparative example, and the resin has excellent performance in the aspects of indentation resistance, fullness, hardness, water resistance and chemical resistance.
From the production practice, the preparation method of the waterborne polyurethane-acrylate resin has the advantages of simple and controllable preparation process, good resistance and indentation resistance, high fullness, low VOC and great practical use value.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (34)
1. A modified waterborne polyurethane resin is characterized in that the modified waterborne polyurethane resin is prepared by the reaction of isocyanate-terminated prepolymer and modified monomer,
the modified monomer comprises at least three of an acrylate monomer, a styrene monomer, tetrahydrofuran acrylate and 3-amino-4, 4, 4-ethyl trifluorocrotonate, and contains the 3-amino-4, 4, 4-ethyl trifluorocrotonate and the tetrahydrofuran acrylate.
2. The polyurethane resin of claim 1, wherein the acrylate monomer comprises one or more of methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, isobornyl acrylate, and isooctyl acrylate;
the styrene monomer comprises one or two of styrene and methyl styrene.
3. The polyurethane resin according to claim 2, wherein the acrylate monomer is methyl methacrylate;
the styrene monomer is styrene.
4. The method of producing a polyurethane resin according to any one of claims 1 to 3, comprising the step of,
mixing and dissolving a modified monomer and an isocyanate-terminated prepolymer, carrying out high-speed shearing dispersion after neutralization reaction to obtain a pre-modified emulsion, and adding an initiator into the pre-modified emulsion to initiate polymerization;
the isocyanate-terminated prepolymer is prepared by mixing and reacting the following raw materials: diisocyanate, macromolecular polyol and a chain extender; the macromolecular polyol comprises at least one of polyether diol and polyester diol.
5. The production method according to claim 4, wherein the mass fractions of the components in the raw materials for producing the isocyanate terminated prepolymer, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin, are: 20-50wt% of diisocyanate and 5-15wt% of chain extender.
6. The production method according to claim 5, wherein the mass fractions of the components in the raw materials for producing the isocyanate terminated prepolymer, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin, are: 30-45wt% of diisocyanate; 8-12wt% of chain extender.
7. The method according to claim 4, wherein the molar ratio of the macromolecular polyol to the diisocyanate is 1:2.5 to 1: 7.
8. The method according to claim 7, wherein the molar ratio of the macromolecular polyol to the diisocyanate is 1:4.5 to 1: 6.5.
9. The method as claimed in claim 4, wherein the polyether diol or polyester diol has a number average molecular weight of 500-3000.
10. The method as claimed in claim 9, wherein the polyether diol or polyester diol has a number average molecular weight of 1000-2000.
11. The production method according to claim 4, wherein the chain extender includes a small-molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender.
12. The production method according to claim 11, wherein the small molecule polyol chain extender is used in an amount of 1 to 5wt% and the carboxylic acid type hydrophilic chain extender is used in an amount of 5 to 10wt%, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin.
13. The production method according to claim 12, wherein the small molecule polyol chain extender is used in an amount of 2 to 4wt% and the carboxylic acid type hydrophilic chain extender is used in an amount of 6 to 9wt%, based on the total mass of the prepolymer for producing the modified aqueous polyurethane resin.
14. The method of claim 11, wherein the small molecule polyol chain extender has a molecular weight of 30 to 200 g/mol.
15. The production method according to claim 11, wherein the carboxylic acid type hydrophilic chain extender is a carboxylic acid type hydrophilic chain extender containing active hydrogen.
16. The method according to claim 4, wherein the modifying monomer is used in an amount of 0.9 to 1.6 times the amount of the isocyanate-terminated prepolymer.
17. The method of claim 16, wherein the modifying monomer is used in an amount of 1.0 to 1.4 times the amount of the isocyanate-terminated prepolymer.
18. The method according to claim 4, wherein the isocyanate terminated prepolymer is diluted and dissolved with a solvent having a boiling point of less than 100 ℃ both at the time of preparing the isocyanate prepolymer and at the time of adding the modifying monomer, and the total amount of the solvent added is 0.8 to 1.2 times the amount of the isocyanate terminated prepolymer.
19. The preparation method according to claim 4, wherein the amount of the initiator is 0.05 to 0.3% by mass of the modified monomer.
20. The preparation method according to claim 19, wherein the amount of the initiator is 0.1 to 0.2% by mass of the modified monomer.
21. The method of claim 20, wherein the initiator comprises an oxidizing agent and a reducing agent.
22. The method of claim 21, wherein the oxidizing agent comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate, and t-butyl hydroperoxide.
23. The method of claim 21, wherein the reducing agent comprises one or more of sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium bisulfite, and erythorbic acid.
24. The method of claim 4, wherein the diisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
25. The method of claim 4, wherein the macropolyol comprises one or more of polyethylene glycol, polypropylene glycol, ethylene oxide/propylene oxide copolyether glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol, and neopentyl glycol adipate 1, 6-hexanediol adipate diol.
26. The method of claim 25, wherein the macropolyol is polytetrahydrofuran ether glycol.
27. The method as claimed in claim 26, wherein the macropolyol is polytetrahydrofuran ether glycol having a number average molecular weight of 1000-2000.
28. The production method according to claim 11, wherein the chain extender includes a small-molecule polyol chain extender and a carboxylic acid type hydrophilic chain extender; the small molecular polyol chain extender comprises one or two of trimethylolpropane and 1, 4-butanediol; the carboxylic acid type hydrophilic chain extender comprises a micromolecular diol compound with a carboxylate radical, and comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid and N, N-dimethylolmaleamic acid.
29. The production method according to claim 4, wherein the reaction temperature used for producing the isocyanate terminated prepolymer is 75 to 85 ℃.
30. The method according to claim 4, wherein the mixing and dissolving of the modifying monomer and the isocyanate terminated prepolymer are carried out at 50 to 60 ℃.
31. The method according to claim 4, wherein the pre-modified emulsion is initiated at a temperature of 30 to 35 ℃.
32. The method of claim 4, further comprising, after the initiating polymerization, the steps of: and removing the solvent in the modified waterborne polyurethane resin obtained by the initiated polymerization.
33. Use of a resin according to any of claims 1 to 3 or a resin prepared by a process according to any of claims 4 to 32 for the preparation of a coating.
34. The use of claim 33, wherein the coating is a wood lacquer coating.
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