CN106883370B - Self-extinction waterborne polyurethane resin with ultralow glossiness and preparation method and application thereof - Google Patents
Self-extinction waterborne polyurethane resin with ultralow glossiness and preparation method and application thereof Download PDFInfo
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- CN106883370B CN106883370B CN201710260865.5A CN201710260865A CN106883370B CN 106883370 B CN106883370 B CN 106883370B CN 201710260865 A CN201710260865 A CN 201710260865A CN 106883370 B CN106883370 B CN 106883370B
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses an ultralow-glossiness self-extinction aqueous polyurethane resin and a preparation method and application thereof. The self-extinction waterborne polyurethane resin with ultralow glossiness is prepared from the following components: s1, at least one aliphatic diisocyanate; s2, at least one oligomeric polyol; s3, at least one triol compound; s4, at least one carboxylic acid type hydrophilic chain extender; s5, at least one catalyst; s6, at least one neutralizing agent; s7, at least one amine sulfonate hydrophilic chain extender; s8, chain extension of at least one small molecule. The ultralow-gloss self-extinction waterborne polyurethane resin has the solid content of 20-40%, the average particle size of 600-4000 nm, no need of adding an extinction agent, simple preparation process, convenience in use, low surface gloss, uniform coating and good stability.
Description
Technical Field
The invention belongs to the field of environment-friendly polyurethane coatings, and particularly relates to an ultralow-gloss self-extinction aqueous polyurethane resin, and a preparation method and application thereof.
Background
With the change of aesthetic concept, the flatting paint is widely used in the surface finishing process of leather, fabric and paper due to the natural appearance, good visual effect and excellent hand feeling of the coating. Heretofore, the direct addition of a matting agent to a coating has been the most widely used method, but since the matting agent is incompatible with a resin, the matting agent tends to agglomerate in the system, so that the coating has poor stability and the surface gloss is not uniform. Inorganic matting agents (such as silica) have excellent matting effect and have disadvantages of large brittleness, poor abrasion resistance and low adhesion strength of the coating film.
The self-extinction waterborne polyurethane is a single-component coating with extinction property, no extinction agent is required to be added in a system, various problems caused by incompatibility of components in the system can be avoided, and the performance of the extinction coating is optimized. Chinese patent CN103740250A discloses a preparation method of a self-extinction leather waterborne polyurethane finishing agent, which is formed by mixing a component A with more branched chains and larger micelle particle size and a component B with small particle size, and has complex preparation process and inconvenient use. The chinese patent CN104974324A prepares a reactive self-extinction aqueous polyurethane resin by a method of controllably producing particles with a certain particle size distribution during the synthesis process, but in the example, the lowest value of 60 ° gloss is 8, and complete extinction cannot be achieved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the self-extinction waterborne polyurethane resin with ultralow glossiness.
The invention also aims to provide a preparation method of the self-extinction waterborne polyurethane resin with ultralow glossiness.
The invention also aims to provide application of the self-extinction waterborne polyurethane resin with ultralow glossiness.
The purpose of the invention is realized by the following technical scheme: an ultralow-gloss self-extinction waterborne polyurethane resin is prepared from the following components:
(A) a prepolymer formed from the following components:
s1, at least one aliphatic diisocyanate, wherein the using amount of the aliphatic diisocyanate is calculated according to the molar ratio (R) of NCO groups to the total amount of hydroxyl groups, and the total amount of the hydroxyl groups is the sum of the hydroxyl groups in oligomer polyol, triol compound and carboxylic acid type hydrophilic chain extender;
s2, at least one oligomeric polyol;
s3, at least one triol compound, wherein the use amount of the triol compound is 0.5-3% of the mass of the prepolymer;
s4, at least one carboxylic acid type hydrophilic chain extender, wherein the using amount of the carboxylic acid type hydrophilic chain extender is 2-5% of the mass of the prepolymer;
s5, at least one catalyst, wherein the using amount of the catalyst is 0.02-0.2% of the mass of the prepolymer;
(B) the prepolymer was neutralized with the following components:
s6, and at least one neutralizing agent, wherein the molar ratio of the neutralizing agent to the carboxylic acid type hydrophilic chain extender is 0.6-1.3: 1;
(C) chain extending the neutralized prepolymer with the following components:
s7, at least one amine sulfonate hydrophilic chain extender, wherein the using amount of the amine sulfonate hydrophilic chain extender is 0.2-2% of the mass of the prepolymer;
s8, and at least one micromolecule chain extender, wherein the dosage of the micromolecule chain extender is calculated according to the molar ratio of the micromolecule chain extender to the theoretical residual NCO group of 0.25-0.6.
The aliphatic diisocyanate of the component S1 is used in an amount calculated according to the molar ratio of NCO groups to the total amount of hydroxyl groups of 1.5-2.1.
The aliphatic diisocyanate described in component S1 is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI).
The molecular weight of the oligomer polyol of the component S2 is 800-3000 g/mol; the oligomer polyalcohol is one or more of polypropylene glycol, polytetrahydrofuran ether glycol, polycarbonate diol, poly epsilon-caprolactone diol, polyethylene glycol adipate diol, polybutylene adipate diol and polyethylene glycol adipate diol.
The amount of the triol compound of the component S3 is 1-2% of the mass of the prepolymer.
The triol compound of the component S3 is one or more of castor oil, triol N330 and trihydroxypropane.
The amount of the carboxylic acid type hydrophilic chain extender of the component S4 is 2.7-3.6% of the mass of the prepolymer, and preferably 2.7-3.3%.
The carboxylic acid type hydrophilic chain extender described in the component S4 is a carboxylic acid type hydrophilic diol, preferably at least one of dimethylolpropionic acid and dimethylolbutyric acid.
The amount of the catalyst of the component S5 is 0.17-0.2% of the mass of the prepolymer.
The catalyst of the component S5 is one or more of dibutyltin dilaurate, stannous octoate and organic bismuth catalysts.
The mole ratio of the neutralizer described in the component S6 to the carboxylic acid type hydrophilic chain extender is preferably 1-1.2: 1.
the neutralizer of the component S6 is one or more of ammonia water, sodium hydroxide and triethylamine.
The use amount of the amine sulfonate hydrophilic chain extender of the component S7 is 0.5-1% of the mass of the prepolymer.
The sulfonate hydrophilic chain extender of the component S7 is ethylenediamine ethanesulfonic acid sodium salt or ethylenediamine propanesulfonic acid sodium salt.
The amount of the micromolecule chain extender of the component S8 is preferably calculated according to the molar ratio of the micromolecule chain extender to the theoretical residual NCO group of 0.4-0.5.
The micromolecular chain extender of the component S8 is one or more of ethylenediamine, hydrazine hydrate and diethylenetriamine.
The preparation method of the self-extinction waterborne polyurethane resin with ultralow glossiness comprises the following steps:
(1) preparation of prepolymer: respectively adding oligomer polyol, a carboxylic acid type hydrophilic chain extender, a triol compound and a catalyst into a reaction vessel, then adding aliphatic diisocyanate at the temperature of 30-65 ℃, and heating to 70-90 ℃ for reaction to obtain a prepolymer;
(2) emulsifying and chain extension: and (2) adding a neutralizer into the prepolymer obtained in the step (1) for neutralization reaction, adding a sulfonate hydrophilic chain extender aqueous solution, carrying out emulsification dispersion and hydrophilic chain extension, and finally adding a small-molecule chain extender for chain extension to obtain the self-extinction waterborne polyurethane resin with ultralow glossiness.
The oligomer polyol described in step (1) is preferably obtained by the following method: and (3) drying the oligomer polyol for 2-4 hours in vacuum at the temperature of 100-130 ℃.
The carboxylic acid type hydrophilic chain extender described in the step (1) is preferably obtained by:
① use organic solvent
Soaking the molecular sieve;
②, drying the carboxylic acid type hydrophilic chain extender in vacuum for 2-4 hours at the temperature of 100-130 ℃;
③ the carboxylic acid type hydrophilic chain extender is dissolved in an organic solvent.
The organic solvent in step ① is N, N-dimethylformamide or N-methylpyrrolidone.
The soaking time described in step ① is preferably one week.
The temperature for adding the aliphatic diisocyanate in the step (1) is preferably 50 ℃.
The reaction time in step (1) is preferably 4 hours, until the NCO group content remains substantially unchanged.
The temperature of the reaction described in step (1) is preferably 85 ℃.
The neutralizing agent in the step (2) is preferably prepared by using a neutralizing agent
Soaking the molecular sieve to obtain the product.
The temperature of the neutralization reaction in the step (2) is preferably 50 ℃ and the time is preferably 20 min.
The emulsification and dispersion in the step (2) are preferably carried out for 30min at 2000 r/min.
The time for adding the small-molecule chain extender for chain extension in the step (2) is preferably 1 h.
The solid content of the ultralow-gloss self-extinction waterborne polyurethane resin is 20-40%, and the preferable solid content is 30%.
The average particle size of the ultralow-gloss self-extinction waterborne polyurethane resin is 600-4000 nm; preferably 1100 to 1600 nm.
The application of the self-extinction waterborne polyurethane resin with ultralow glossiness in the field of polyurethane coatings.
Compared with the prior art, the invention has the following advantages and effects:
1. the invention provides the self-extinction waterborne polyurethane resin with the ultralow glossiness and the preparation method thereof, the polyurethane body can realize the low glossiness (the glossiness at 60 degrees is less than or equal to 1) on the surface without adding a flatting agent, and the self-extinction waterborne polyurethane resin has uniform coating and good stability. When the using amount of the hydrophilic group (carboxyl in the carboxylic acid type hydrophilic chain extender and sulfonic group in the sulfonate hydrophilic chain extender) is slightly larger, the average particle size is slightly smaller, and the glossiness is more than 1, but is far lower than that of the existing polyurethane.
2. The invention adopts proper raw material proportion and process conditions to prepare the waterborne polyurethane emulsion with the average particle size of 600-4000 nm, wherein the solid content of the resin is 20-40%.
3. In the prior art, the triol compound is rarely used for preparing the aqueous polyurethane resin, because the triol can cause the viscosity of the prepolymer to be too high and is difficult to emulsify; in the invention, the trihydric alcohol can effectively realize low surface gloss, and the dosage of all raw materials including the trihydric alcohol is continuously optimized, so that the self-dulling waterborne polyurethane emulsion is successfully prepared.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the ultralow-gloss self-extinction aqueous polyurethane resin prepared by the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of an aqueous polyurethane resin prepared without adding a triol.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
1. Pretreatment of raw materials
(1) Vacuum drying the oligomer polyol and the carboxylic acid type hydrophilic chain extender at the temperature of 100-130 ℃ for 2-4 hours for later use;
(2) respectively using neutralizing agent and organic solvent (N, N-dimethylformamide or N-methylpyrrolidone)Soaking the molecular sieve for one week for later use;
(3) the carboxylic acid type hydrophilic chain extender is dissolved in the organic solvent in advance for standby.
Note:
1. in the examples, R is a molar ratio of NCO groups (NCO groups of aliphatic diisocyanate) to the total amount of OH (total amount of OH in the oligomer polyol, triol compound and carboxylic acid type hydrophilic chain extender), that is, R ═ N (NCO)/n (total amount of OH).
2. The neutralization degree is the mole percentage of the neutralizing agent to the anionic hydrophilic chain extender (carboxylic acid type hydrophilic chain extender).
Example 1
1. The proportion of the ultralow-gloss self-extinction waterborne polyurethane resin is as follows:
(a) r ═ 1.5; (b) the mass fraction of the dimethylolbutyric acid in the prepolymer is 3.3%; (c) the neutralization degree is 120%; (d) the trimethylolpropane accounts for 1 percent of the mass fraction of the prepolymer; (e) dibutyltin dilaurate accounts for 0.17% of the mass fraction of the prepolymer; (f) the mass fraction of the ethylenediamine sodium ethanesulfonate in the prepolymer is 1%; (g) hydrazine hydrate reaction active group (the reaction active group is NH in micromolecular chain extender)2The radical, hydrazine hydrate, having two NH groups2Group) to the theoretical residual NCO by mole ratio of 1; (h) the solid content of the resin was 30%.
2. The preparation method of the self-extinction waterborne polyurethane resin with ultralow glossiness comprises the following steps:
(1) 50g of polytetrahydrofuran ether glycol (molecular weight: 1000), 2.37g of dimethylolbutyric acid (previously dissolved with 5g of DMF), 0.72g of trimethylolpropane and 0.12g of dibutyltin dilaurate were separately added to a reaction vessel, and 18.67g of hexamethylene diisocyanate was added at 50 ℃ followed by slowly raising the temperature to 85 ℃ and continuing the reaction for about 4 hours to obtain a prepolymer.
(2) Cooling the prepolymer to 50 ℃, neutralizing the prepolymer for 20min by using 1.94g of triethylamine, then adding 130mL of water containing 1.44g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution (the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt is 50 percent), namely, 0.72g of pure ethylenediamine ethanesulfonic acid sodium salt in the 1.44g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution) to carry out emulsification and dispersion for 30min at the rotating speed of 2000r/min, and finally adding 35mL of water containing 2.0g of ethylenediamine to carry out chain extension for 1h, thus obtaining the self-extinction aqueous polyurethane emulsion with ultralow glossiness.
The average particle diameter of the aqueous polyurethane prepared in example 1 was 1309nm, and the 60 ℃ gloss was 0.7.
Example 2
1. The proportion of the ultralow-gloss self-extinction waterborne polyurethane resin is as follows:
(a) r ═ 1.9; (b) the mass fraction of the dimethylolbutyric acid in the prepolymer is 3.6%; (c) the neutralization degree is 120%; (d) the trimethylolpropane accounts for 2 percent of the mass fraction of the prepolymer; (e) dibutyltin dilaurate accounts for 0.17% of the mass fraction of the prepolymer; (f) the mass fraction of the ethylenediamine sodium ethanesulfonate in the prepolymer is 0.5%; (g) ethylene diamine reactive group (the reactive group is NH in the micromolecular chain extender)2Radical, ethylenediamine having two NH groups2Group) to the theoretical residual NCO by mole ratio of 1; (h) the solid content of the resin is 30 percent;
2. the preparation method of the self-extinction waterborne polyurethane resin with ultralow glossiness comprises the following steps:
(1) 50g of polytetrahydrofuran ether diol (molecular weight: 1000), 2.99g of dimethylolbutyric acid (previously dissolved with 5g of DMF), 1.66g of trimethylolpropane and 0.14g of dibutyltin dilaurate were separately added to a reaction vessel, and 28.37g of hexamethylene diisocyanate was added at 50 ℃ followed by slowly raising the temperature to 85 ℃ and continuing the reaction for about 4 hours to obtain a prepolymer.
(2) Cooling the prepolymer to 50 ℃, neutralizing the prepolymer for 20min by using 2.45g of triethylamine, then adding 150mL of water containing 0.83g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution (the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt is 50 percent), namely 0.415g of ethylenediamine ethanesulfonic acid sodium salt in the 0.83g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution), emulsifying and dispersing for 30min at the rotating speed of 2000r/min, and finally adding 45mL of water containing 4.54g of ethylenediamine for chain extension for 1h to obtain the self-extinction aqueous polyurethane emulsion with ultralow glossiness.
The average particle diameter of the aqueous polyurethane prepared in example 2 was 1032nm, and the 60 ℃ gloss was 1.6.
Example 3
1. The proportion of the ultralow-gloss self-extinction waterborne polyurethane resin is as follows:
(a) r ═ 2.1; (b) the mass fraction of dimethylolpropionic acid in the prepolymer was 2.7%; (c) the neutralization degree is 100 percent; (d) the trimethylolpropane accounts for 1.5 percent of the mass fraction of the prepolymer; (e) the organic bismuth catalyst accounts for 0.2 percent of the mass fraction of the prepolymer; (f) the mass fraction of the ethylenediamine sodium ethanesulfonate in the prepolymer is 0.5%; (g) the molar ratio of the equivalent weight of the hydrazine hydrate reactive group to the theoretical residual NCO is 0.8; (h) the solid content of the resin is 30 percent;
2. the preparation method of the self-extinction waterborne polyurethane resin with ultralow glossiness comprises the following steps:
(1) 50g of polyethylene glycol adipate polyol (molecular weight 1000), 2.54g of dimethylolpropionic acid (previously dissolved with 5g of DMF), 1.41g of trimethylolpropane and 0.19g of organobismuth catalyst were added to a reaction vessel, respectively, and 39.57g of isophorone diisocyanate was added at 50 ℃ followed by slowly raising the temperature to 85 ℃ and continuing the reaction for about 4 hours to obtain a prepolymer.
(2) Cooling the prepolymer to 50 ℃, neutralizing the prepolymer for 20min by using 1.92g of triethylamine, then adding 170mL of water containing 0.95g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution (the mass fraction of the ethylenediamine ethanesulfonic acid sodium salt is 50 percent), namely 0.475g of ethylenediamine ethanesulfonic acid sodium salt in the 0.95g of ethylenediamine ethanesulfonic acid sodium salt aqueous solution), emulsifying and dispersing for 30min at the rotating speed of 2000r/min, and finally adding 45mL of water containing 4.51g of hydrazine hydrate for chain extension for 1h to obtain the self-extinction aqueous polyurethane emulsion with ultralow glossiness.
The average particle diameter of the aqueous polyurethane prepared in example 3 was 1524nm, and the 60 ℃ gloss was 0.8.
Comparative example 1
1. The method is the same as example 1, the self-extinction waterborne polyurethane with ultralow glossiness is prepared, and the surface appearance of the self-extinction waterborne polyurethane is observed under a scanning electron microscope.
2. Referring to the preparation method of example 1, the surface morphology of the aqueous polyurethane prepared without adding a triol compound (trimethylolpropane) was observed under a scanning electron microscope for comparison.
The results are shown in fig. 1 and fig. 2, wherein fig. 1 shows that the ultralow-gloss self-extinction waterborne polyurethane prepared by adding the triol compound is formed by tightly piling spherical particles on the surface, has strong scattering effect on light and has low gloss (the 60-degree gloss is less than or equal to 1); FIG. 2 shows that the surface gloss of the aqueous polyurethane is high (60 ℃ gloss is not less than 20) without the addition of a triol compound.
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 (10)
1. The self-extinction waterborne polyurethane resin with ultralow glossiness is characterized by being prepared from the following components:
(A) a prepolymer formed from the following components:
s1, at least one aliphatic diisocyanate, wherein the using amount of the aliphatic diisocyanate is calculated according to the molar ratio of NCO groups to the total amount of hydroxyl groups of 1.2-2.4, and the total amount of the hydroxyl groups is the sum of the hydroxyl groups in oligomer polyol, triol compound and carboxylic acid type hydrophilic chain extender;
s2, at least one oligomeric polyol;
s3, at least one triol compound, wherein the use amount of the triol compound is 0.5-3% of the mass of the prepolymer;
s4, at least one carboxylic acid type hydrophilic chain extender, wherein the using amount of the carboxylic acid type hydrophilic chain extender is 2-5% of the mass of the prepolymer;
s5, at least one catalyst, wherein the using amount of the catalyst is 0.02-0.2% of the mass of the prepolymer;
(B) the prepolymer was neutralized with the following components:
s6, and at least one neutralizing agent, wherein the molar ratio of the neutralizing agent to the carboxylic acid type hydrophilic chain extender is 0.6-1.3: 1;
(C) chain extending the neutralized prepolymer with the following components:
s7, at least one amine sulfonate hydrophilic chain extender, wherein the using amount of the amine sulfonate hydrophilic chain extender is 0.2-2% of the mass of the prepolymer;
s8, at least one micromolecule chain extender, wherein the dosage of the micromolecule chain extender is calculated according to the molar ratio of the micromolecule chain extender to the theoretical residual NCO group of 0.25-0.6;
the 60-degree glossiness of the obtained waterborne polyurethane resin is less than or equal to 1.6.
2. The ultra-low gloss self-matting aqueous polyurethane resin according to claim 1 wherein:
the amount of the aliphatic diisocyanate of the component S1 is calculated according to the molar ratio of NCO groups to the total amount of hydroxyl groups being 1.5-2.1;
the amount of the triol compound as the component S3 is 1-2% of the mass of the prepolymer;
the using amount of the carboxylic acid type hydrophilic chain extender of the component S4 is 2.7-3.6% of the mass of the prepolymer;
the amount of the catalyst of the component S5 is 0.17-0.2% of the mass of the prepolymer;
the mole ratio of the neutralizer described in the component S6 to the carboxylic acid type hydrophilic chain extender is 1-1.2: 1;
the use amount of the amine sulfonate hydrophilic chain extender of the component S7 is 0.5-1% of the mass of the prepolymer;
the dosage of the micromolecule chain extender of the component S8 is calculated according to the molar ratio of the micromolecule chain extender to the theoretical residual NCO group of 0.4-0.5.
3. The ultralow-gloss self-matting aqueous polyurethane resin according to claim 1 or 2, wherein: the triol compound of the component S3 is one or more of castor oil, triol N330 and trimethylolpropane.
4. The ultra-low gloss self-matting aqueous polyurethane resin according to claim 1 wherein: the molecular weight of the oligomer polyol of the component S2 is 800-3000 g/mol.
5. The ultra-low gloss self-matting aqueous polyurethane resin according to claim 1 wherein:
the aliphatic diisocyanate described in the component S1 is one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the oligomer polyol of the component S2 is one or more of polypropylene glycol, polytetrahydrofuran ether glycol, polycarbonate glycol, poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, polybutylene adipate glycol and polyethylene glycol adipate glycol;
the carboxylic acid type hydrophilic chain extender described in the component S4 is carboxylic acid type hydrophilic dihydric alcohol.
6. The ultralow-gloss self-matting aqueous polyurethane resin according to claim 1 or 2, wherein:
the sulfonate hydrophilic chain extender of the component S7 is ethylenediamine ethanesulfonic acid sodium salt or ethylenediamine propanesulfonic acid sodium salt;
the micromolecular chain extender of the component S8 is one or more of ethylenediamine, hydrazine hydrate and diethylenetriamine.
7. The ultralow-gloss self-matting aqueous polyurethane resin according to claim 1 or 2, wherein:
the catalyst of the component S5 is one or more of dibutyltin dilaurate, stannous octoate and an organic bismuth catalyst;
the neutralizer of the component S6 is one or more of ammonia water, sodium hydroxide and triethylamine.
8. The preparation method of the ultralow-gloss self-extinction aqueous polyurethane resin according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) preparation of prepolymer: respectively adding oligomer polyol, a carboxylic acid type hydrophilic chain extender, a triol compound and a catalyst into a reaction vessel, then adding aliphatic diisocyanate at the temperature of 30-65 ℃, and heating to 70-90 ℃ for reaction to obtain a prepolymer;
(2) emulsifying and chain extension: and (2) adding a neutralizer into the prepolymer obtained in the step (1) for neutralization reaction, adding a sulfonate hydrophilic chain extender aqueous solution, carrying out emulsification dispersion and hydrophilic chain extension, and finally adding a small-molecule chain extender for chain extension to obtain the self-extinction waterborne polyurethane resin with ultralow glossiness.
9. The method for preparing the self-extinction aqueous polyurethane resin with ultralow glossiness according to claim 8, wherein the method comprises the following steps:
the oligomer polyol described in step (1) is obtained by the following method: vacuum drying the oligomer polyol at the temperature of 100-130 ℃ for 2-4 h;
the reaction time in the step (1) is 4 h;
the reaction temperature in the step (1) is 85 ℃;
the temperature of the neutralization reaction in the step (2) is 50 ℃, and the time is 20 min;
the emulsification and dispersion in the step (2) are carried out for 30min at 2000 r/min;
and (3) adding a micromolecular chain extender for chain extension in the step (2) for 1 h.
10. The use of the ultralow-gloss self-extinction aqueous polyurethane resin according to any one of claims 1 to 7 in the field of polyurethane coatings.
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| CN108165152A (en) * | 2017-12-27 | 2018-06-15 | 广东德冠薄膜新材料股份有限公司 | A kind of anti-scraping coating of aqueous low and hoarse light and its application method |
| CN108546323B (en) * | 2018-04-18 | 2020-08-28 | 万华化学集团股份有限公司 | Cation self-extinction resin and preparation method and application thereof |
| CN108794723A (en) * | 2018-04-23 | 2018-11-13 | 合肥科天水性科技有限责任公司 | A kind of biology base dumb light aqueous polyurethane dispersion and preparation method thereof |
| CN109180901A (en) * | 2018-08-23 | 2019-01-11 | 洛阳盛嘉新材料有限公司 | From delustring aqueous polyurethane and preparation method thereof |
| CN109206588A (en) * | 2018-08-23 | 2019-01-15 | 洛阳盛嘉新材料有限公司 | High solid amount contains big partial size from delustring aqueous polyurethane and preparation method thereof |
| CN109796574A (en) * | 2018-12-26 | 2019-05-24 | 浙江深蓝新材料科技有限公司 | The aqueous preparation method from matting resin |
| CN111944111B (en) * | 2019-04-30 | 2022-04-22 | 万华化学集团股份有限公司 | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof |
| CN110204682B (en) | 2019-06-01 | 2020-06-16 | 上海思盛聚合物材料有限公司 | Aqueous polyurethane dispersions containing reactive nonionic emulsifiers and sulfonate groups |
| CN110423329A (en) * | 2019-08-29 | 2019-11-08 | 江苏宝泽高分子材料股份有限公司 | One kind is from extinction type waterborne polyurethane resin and preparation method thereof |
| CN110951039A (en) * | 2019-11-24 | 2020-04-03 | 华南理工大学 | Environment-friendly self-extinction waterborne polyurethane and preparation method and application thereof |
| CN111848914A (en) * | 2020-06-10 | 2020-10-30 | 华南理工大学 | Self-extinction light-cured waterborne polyurethane acrylate cured film with low water absorption rate and preparation method and application thereof |
| CN113637141B (en) * | 2021-06-17 | 2023-03-28 | 厦门威亮光学涂层技术有限公司 | Internal crosslinking type self-extinction aqueous polyurethane dispersion and preparation method thereof |
| CN114940864B (en) * | 2022-05-10 | 2023-08-29 | 南通市建筑设计研究院有限公司 | Kindergarten wall based on novel erasable coating |
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