CN115058176A - Epoxy modified self-extinction waterborne polyurethane emulsion and preparation method thereof - Google Patents
Epoxy modified self-extinction waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyurethane emulsion, and particularly relates to epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 85.5-96 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 0.5-2 wt% of thickening agent, 2-5 wt% of cross-linking agent, 0.5-1 wt% of wetting agent, 0.5-1 wt% of hand feeling agent and 0.1-0.5 wt% of defoaming agent; the epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight: 10-20.5 parts of dihydric alcohol, 5.5-8.5 parts of diisocyanate, 0.002-0.04 part of catalyst, 0.08-0.4 part of hydrophilic chain extender, 0.01-0.2 part of epoxy resin, 0.1-0.2 part of neutralizer and 0.5-0.8 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.7-2, the amount of the hydrophilic chain extender accounts for 0.8-2% of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1-1.2. The invention provides an epoxy modified self-extinction waterborne polyurethane emulsion, and epoxy resin is adopted for modification in a prepolymer stage, so that various performances of the emulsion after film coating are obviously improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane emulsion, and particularly relates to epoxy modified self-extinction aqueous polyurethane emulsion and a preparation method thereof.
Background
With the improvement of living standard of people, people pay more and more attention to pursuit of living quality, in certain industries such as fields of plastic replacing oil, PVC coating, gravure ink, touch feeling oil, leather finishing agent and the like, the soft color and the matte effect can bring elegant and comfortable feeling to people due to strong texture, and the people are more and more favored and pursued by consumers.
In order to achieve the matte effect, the traditional method is to add matting powder such as fumed silica, paraffin or polyolefin powder, and some metal soaps and functional fine materials to achieve the matting purpose, but the process usually has the following technical defects: 1. a large amount of dust pollution exists in the production process; 2. after the extinction treatment is carried out on the powder, the coating is high in brittleness and easy to break and fall off, and the scratch resistance, folding resistance and the like of the coating film are affected.
In recent years, a single-component WPU (waterborne polyurethane) matt resin is attracted by the coating industry, does not use any matting agent at all, only generates microspheres similar to the matting agent in the synthesis process, and increases the surface roughness of the microspheres in the drying process of a paint film so as to achieve the aim of matting. However, hydrophilic monomers and linear molecular structures need to be introduced into self-emulsifying light-eliminating waterborne polyurethane, so that the water resistance and solvent resistance of a coating film are poor, and the hardness of the formed film of an adhesive film is generally low.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides an epoxy modified self-extinction aqueous polyurethane emulsion, in the synthesis process of a prepolymer, epoxy resin is adopted for modification, a large amount of epoxy groups in the epoxy resin react with active hydrogen on amino groups in the polyurethane prepolymer to open loops to generate hydroxyl groups, the generated hydroxyl groups and the hydroxyl groups on epoxy molecules simultaneously react with-NCO groups in isocyanic acid to form a cross-linked network structure, so that the cross-linking density of the emulsion can be further improved, and the hardness, the water resistance and the solvent resistance of a glue film are improved; meanwhile, the molecular structure of the bisphenol A epoxy resin contains a large number of ether bonds, benzene rings and other groups, so that the hardness of the adhesive film can be improved, and the toughness of the adhesive film can be effectively balanced, thereby improving the scratch resistance and the folding resistance of the adhesive film. On the other hand, when the emulsion formula auxiliary agent is added, the cross-linking agent is added, so that the adhesive film performance can be greatly improved, and the room-temperature storage property of the single-component waterborne polyurethane is not influenced. The invention also provides a preparation method of the epoxy modified self-extinction aqueous polyurethane emulsion, which has simple process steps and high finished product preparation efficiency.
The technical effect to be achieved by the invention is realized by the following technical scheme:
the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following components in percentage by weight: 85.5-96 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 0.5-2 wt% of thickening agent, 2-5 wt% of cross-linking agent, 0.5-1 wt% of wetting agent, 0.5-1 wt% of hand feeling agent and 0.1-0.5 wt% of defoaming agent; the epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight: 10-20.5 parts of dihydric alcohol, 5.5-8.5 parts of diisocyanate, 0.002-0.04 part of catalyst, 0.08-0.4 part of hydrophilic chain extender, 0.01-0.2 part of epoxy resin, 0.1-0.2 part of neutralizer and 0.5-0.8 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.7-2, the amount of the hydrophilic chain extender accounts for 0.8-2% of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1-1.2.
As a preferable scheme, the dihydric alcohol is one or a mixture of more of polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate dihydric alcohol, poly 1, 4-butanediol adipate dihydric alcohol and poly neopentyl glycol adipate 1, 6-hexanediol adipate dihydric alcohol. The macromolecule polycarbonate dihydric alcohol can improve the crystallinity of the prepolymer and effectively improve the strength of the prepolymer; the polyethylene glycol has good hydrophilicity, which is beneficial to improving the transparency of the prepolymer; preferably, the diols are polycarbonates and polytetrahydrofuran diols, Wn 1000 g/mol.
In a preferred embodiment, the diisocyanate is a mixture of one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4, 4-dicyclohexyl dimethylamine diisocyanate. The hexamethylene diisocyanate is of a linear symmetrical structure, is relatively compact in arrangement and good in flexibility, and is beneficial to improving the flexibility and the water resistance of the formed waterborne polyurethane adhesive film; the isophorone diisocyanate is of a ring structure, has high rigidity, and is favorable for the heat resistance and the strength of the formed waterborne polyurethane adhesive film; preferably, the hexamethylene diisocyanate accounts for not less than 14.5% of the total mass of the diisocyanates.
As a preferable scheme, the epoxy resin is bisphenol A epoxy resin or polyfunctional epoxy diluent.
As a preferable scheme, the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid, and dimethylolbutyric acid with better solubility is preferable.
As a preferable scheme, the amine chain extender is isophorone diamine, ethylene diamine or hydrazine hydrate; preferably hydrazine hydrate is subjected to post-chain extension, so that the yellowing resistance of the emulsion is improved.
As a preferred embodiment, the catalyst is an organobismuth catalyst.
As a preferable scheme, the neutralizing agent is triethylamine or dimethylethanolamine, and dimethylethanolamine is preferably used for neutralization.
Preferably, the thickener is one or more of hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylic acid, polyacrylate, polyurethane, and high molecular weight polyethylene oxide.
In a preferred embodiment, the wetting agent is a polyether modified silicone wetting agent.
In a preferred embodiment, the defoaming agent is a polyether modified silicone defoaming agent.
In a preferred embodiment, the crosslinking agent is any one of a carbodiimide crosslinking agent, aziridine, polyisocyanate, and epoxy silane, and is preferably an epoxy silane crosslinking agent.
As one of the preferable schemes, the hand feeling agent is siloxane with the molecular weight of 1000-30000, and the large molecular weight siloxane with the molecular weight of 30000 is preferable.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a predetermined amount of dihydric alcohol under the conditions of high temperature and vacuum;
pre-polymerization: cooling the dried dihydric alcohol to 60-70 ℃, adding diisocyanate and a catalyst, heating to 80-100 ℃, reacting for 1-2h, controlling the-NCO content to reach a preset theoretical value, and cooling to 40-60 ℃ again; adding epoxy resin, a hydrophilic chain extender and acetone, uniformly stirring, heating to 75-85 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding a neutralizing agent, stirring for 10-20min for neutralization, then adjusting the rotating speed to high-speed stirring, adding metered deionized water, and stirring at high speed for 15 min;
and (3) finished product: adding amine chain extender, reacting at the temperature of 30-40 ℃ for 10-30 min, and removing acetone by vacuum distillation to obtain the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 85.5-96 wt%; adding a predetermined amount of thickening agent, cross-linking agent, hand feeling agent and defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
As a preferable scheme, in the drying step, a predetermined amount of glycol is dried for 1-2h at the temperature of 100 ℃ and 120 ℃ and under the vacuum degree of-0.08 MPa.
In summary, the invention has at least the following advantages:
1. according to the epoxy modified self-extinction waterborne polyurethane emulsion, epoxy resin is adopted for modification in a prepolymer stage, and the epoxy resin not only enables a high molecular chain to be crosslinked in a reaction stage, but also introduces rigid groups on epoxy groups, so that the hardness of a system can be effectively improved, the hardness of polyurethane emulsion particles is further improved, the stability of the emulsion particles is kept when the polyurethane emulsion particles are dried to form a film, and the glossiness cannot be greatly changed.
2. According to the epoxy modified self-extinction waterborne polyurethane emulsion, in the process of drying the polyurethane emulsion to form a film, the epoxy silane cross-linking agent is added during emulsion compounding, so that the molecular weight of a system is further improved, and the scratch resistance and folding resistance of a glue film can be effectively improved; and the epoxy silane crosslinking agent is used in the single-component waterborne polyurethane, so that the storage stability is not negatively influenced.
Detailed Description
In a first aspect, the invention provides an epoxy modified self-extinction aqueous polyurethane emulsion, which comprises the following components in percentage by weight: 85.5-96 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 0.5-2 wt% of thickening agent, 2-5 wt% of cross-linking agent, 0.5-1 wt% of wetting agent, 0.5-1 wt% of hand feeling agent and 0.1-0.5 wt% of defoaming agent; the epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight: 10-20.5 parts of dihydric alcohol, 5.5-8.5 parts of diisocyanate, 0.002-0.04 part of catalyst, 0.08-0.4 part of hydrophilic chain extender, 0.01-0.2 part of epoxy resin, 0.1-0.2 part of neutralizer and 0.5-0.8 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.7-2, the amount of the hydrophilic chain extender accounts for 0.8-2% of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1-1.2.
Further, the dihydric alcohol is one or a mixture of more of polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate dihydric alcohol, 1, 4-butanediol adipate dihydric alcohol and neopentyl glycol adipate 1, 6-hexanediol adipate dihydric alcohol. The diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and 4, 4-dicyclohexyl dimethylamine diisocyanate. The epoxy resin is bisphenol A type epoxy resin or polyfunctional epoxy diluent; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the amine chain extender is isophorone diamine, ethylene diamine or hydrazine hydrate. The catalyst is an organic bismuth catalyst; the neutralizing agent is triethylamine or dimethylethanolamine.
The thickener is one or more of hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylic acid, polyacrylate, polyurethane and high molecular weight polyethylene oxide; the wetting agent is polyether modified organic silicon wetting agent; the defoaming agent is polyether modified organic silicon defoaming agent; the cross-linking agent is any one of a carbodiimide cross-linking agent, aziridine, polyisocyanate and epoxy silane; the hand feeling agent is siloxane with the molecular weight of 1000-30000.
In a second aspect, the preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a predetermined amount of dihydric alcohol under the conditions of high temperature and vacuum;
prepolymerization: cooling the dried dihydric alcohol to 60-70 ℃, adding diisocyanate and a catalyst, heating to 80-100 ℃, reacting for 1-2h, controlling the-NCO content to reach a preset theoretical value, and cooling to 40-60 ℃ again; adding epoxy resin, a hydrophilic chain extender and acetone, uniformly stirring, heating to 75-85 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding a neutralizing agent, stirring for 10-20min for neutralization, then adjusting the rotating speed to high-speed stirring, adding metered deionized water, and stirring at high speed for 15 min;
and (3) finished product: adding amine chain extender, reacting at the temperature of 30-40 ℃ for 10-30 min, and removing acetone by vacuum distillation to obtain the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 85.5-96 wt%; adding a predetermined amount of thickening agent, cross-linking agent, hand feeling agent and defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Further, in the drying step, a predetermined amount of glycol is dried for 1-2h at the temperature of 100 ℃ and 120 ℃ and under the vacuum degree of-0.08 MPa or less.
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 90 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 1 wt% of hydroxyethyl cellulose, 2.5 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organic silicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organic silicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
15 parts of dihydric alcohol, 6.5 parts of diisocyanate, 0.01 part of catalyst, 0.15 part of hydrophilic chain extender, 0.1 part of epoxy resin, 0.15 part of neutralizer and 0.6 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.8, the amount of the hydrophilic chain extender accounts for 1 percent of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1.1. Preferably, the diol comprises 11.5 parts polycarbonate diol and 3.5 parts polytetrahydrofuran ether glycol, and the diisocyanate comprises 1.5 parts HDI and 5 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 11.5 parts of polycarbonate diol and 3.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of the polycarbonate diol and the polytetrahydrofuran ether glycol to 70 ℃, adding 1.5 parts of HDI, 5 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃ for reaction for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.1 part of bisphenol A type epoxy resin, 0.15 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.15 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 35 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.6 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and obtaining the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 90 wt% after vacuumizing and distilling to remove acetone; adding 1 wt% of hydroxyethyl cellulose, 2.5 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Example 2:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 85.5 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 0.5 wt% of hydroxyethyl cellulose, 2 wt% of epoxy silane cross-linking agent, 0.5 wt% of polyether modified organic silicon wetting agent, 0.5 wt% of high molecular weight siloxane and 0.1 wt% of polyether modified organic silicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
10 parts of dihydric alcohol, 5.5 parts of diisocyanate, 0.002 part of catalyst, 0.08 part of hydrophilic chain extender, 0.01 part of epoxy resin, 0.1 part of neutralizer and 0.5 part of amine chain extender; the R value before the dispersion chain extension is 1.7, the use amount of the hydrophilic chain extender accounts for 0.8 percent of the total mass of the dispersion, and the R value after the dispersion chain extension is 1. Preferably, the diol comprises 9.5 parts of polycaprolactone diol and 0.5 part of polyethylene glycol monomethyl ether, and the diisocyanate comprises 1 part of HDI and 4.5 parts of HMDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 6.5 parts of polycarbonate diol and 3.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of polycaprolactone diol and polyethylene glycol monomethyl ether to 70 ℃, adding 1 part of HDI, 4.5 parts of HMDI and 0.002 part of organic bismuth catalyst, heating to 90 ℃, reacting for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.01 part of bisphenol A epoxy resin, 0.08 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.1 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 33.5 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.5 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and removing acetone by vacuum distillation to obtain an epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 85.5 wt%; adding 0.5 wt% of hydroxyethyl cellulose, 2 wt% of epoxy silane cross-linking agent, 0.5 wt% of polyether modified organosilicon wetting agent, 0.5 wt% of high molecular weight siloxane and 0.1 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Example 3:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 92 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 1.5 wt% of hydroxyethyl cellulose, 4 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organic silicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.3 wt% of polyether modified organic silicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
18 parts of dihydric alcohol, 7.5 parts of diisocyanate, 0.02 part of catalyst, 0.25 part of hydrophilic chain extender, 0.15 part of epoxy resin, 0.15 part of neutralizer and 0.7 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.9, the amount of the hydrophilic chain extender accounts for 1.5 percent of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1.1. Preferably, the diol comprises 14 parts polycarbonate diol and 4 parts polytetrahydrofuran ether glycol, the diisocyanate comprises 2 parts HDI and 5.5 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 14 parts of polycarbonate diol and 4 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of the polycarbonate diol and the polytetrahydrofuran ether glycol to 70 ℃, adding 2 parts of HDI, 5.5 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃ for reaction for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.15 part of bisphenol A epoxy resin, 0.25 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.15 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 35 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.7 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and obtaining the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 92 wt% after vacuumizing and distilling to remove acetone; adding 1.5 wt% of hydroxyethyl cellulose, 4 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.3 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Example 4:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 96 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 2 wt% of hydroxyethyl cellulose, 5 wt% of epoxy silane cross-linking agent, 1 wt% of polyether modified organic silicon wetting agent, 1 wt% of high molecular weight siloxane and 0.5 wt% of polyether modified organic silicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
20.5 parts of dihydric alcohol, 8.5 parts of diisocyanate, 0.04 part of catalyst, 0.4 part of hydrophilic chain extender, 0.2 part of epoxy resin, 0.2 part of neutralizer and 0.8 part of amine chain extender; wherein the R value of the dispersion before chain extension is 2, the amount of the hydrophilic chain extender accounts for 2 percent of the total mass of the dispersion, and the R value of the dispersion after chain extension is 1.2. Preferably, the diol comprises 16 parts polycarbonate diol and 4.5 parts polytetrahydrofuran ether glycol, the diisocyanate comprises 2.5 parts HDI and 6 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 16 parts of polycarbonate diol and 4.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 MPa;
prepolymerization: cooling the dried mixture of polycarbonate diol and polytetrahydrofuran ether glycol to 70 ℃, adding 2.5 parts of HDI, 6 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃, reacting for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.2 part of bisphenol A epoxy resin, 0.4 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.2 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 35 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.8 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and obtaining an epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 96 wt% after vacuumizing and distilling to remove acetone; adding 2 wt% of hydroxyethyl cellulose, 5 wt% of epoxy silane cross-linking agent, 1 wt% of polyether modified organosilicon wetting agent, 1 wt% of high molecular weight siloxane and 0.5 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Comparative example 1:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 90 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 1 wt% of hydroxyethyl cellulose, 2.5 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organosilicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
15 parts of dihydric alcohol, 6.5 parts of diisocyanate, 0.01 part of catalyst, 0.15 part of hydrophilic chain extender, 0.15 part of neutralizer and 0.6 part of amine chain extender; preferably, the diol comprises 11.5 parts polycarbonate diol and 3.5 parts polytetrahydrofuran ether glycol, and the diisocyanate comprises 1.5 parts HDI and 5 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 11.5 parts of polycarbonate diol and 3.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of the polycarbonate diol and the polytetrahydrofuran ether glycol to 70 ℃, adding 1.5 parts of HDI, 5 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃ for reaction for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.15 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.15 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 35 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.6 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and vacuumizing and distilling to remove acetone to obtain an epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 90 wt%; adding 1 wt% of hydroxyethyl cellulose, 2.5 wt% of epoxy silane cross-linking agent, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
Comparative example 2:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 90 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 1 wt% of hydroxyethyl cellulose, 0.8 wt% of polyether modified organic silicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organic silicon defoamer.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
15 parts of dihydric alcohol, 6.5 parts of diisocyanate, 0.01 part of catalyst, 0.15 part of hydrophilic chain extender, 0.1 part of epoxy resin, 0.15 part of neutralizer and 0.6 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.8, the amount of the hydrophilic chain extender accounts for 1 percent of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1.1. Preferably, the diol comprises 11.5 parts polycarbonate diol and 3.5 parts polytetrahydrofuran ether glycol, and the diisocyanate comprises 1.5 parts HDI and 5 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion comprises the following steps:
and (3) drying: drying a mixture of 11.5 parts of polycarbonate diol and 3.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of the polycarbonate diol and the polytetrahydrofuran ether glycol to 70 ℃, adding 1.5 parts of HDI, 5 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃ for reaction for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.1 part of bisphenol A type epoxy resin, 0.15 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.15 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotation speed to high-speed stirring, adding 35 parts of deionized water, and stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.6 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and vacuumizing and distilling to remove acetone to obtain an epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 90 wt%; adding 1 wt% of hydroxyethyl cellulose, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction waterborne polyurethane emulsion.
Comparative example 3:
the embodiment provides an epoxy modified self-extinction aqueous polyurethane emulsion which comprises the following components in percentage by weight: 90 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 1 wt% of hydroxyethyl cellulose, 0.8 wt% of polyether modified organic silicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organic silicon defoaming agent.
The epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
15 parts of dihydric alcohol, 6.5 parts of diisocyanate, 0.01 part of catalyst, 0.15 part of hydrophilic chain extender, 0.15 part of neutralizer and 0.6 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.8, the amount of the hydrophilic chain extender accounts for 1 percent of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1.1. Preferably, the diol comprises 11.5 parts polycarbonate diol and 3.5 parts polytetrahydrofuran ether glycol, and the diisocyanate comprises 1.5 parts HDI and 5 parts IPDI; the hydrophilic chain extender is 2, 2-dimethylolpropionic acid, the epoxy resin is bisphenol A epoxy resin, the neutralizer is triethylamine, the amine chain extender is isophorone diamine, and the catalyst is an organic bismuth catalyst.
The preparation method of the epoxy modified self-extinction waterborne polyurethane emulsion in the embodiment comprises the following steps:
and (3) drying: drying a mixture of 11.5 parts of polycarbonate diol and 3.5 parts of polytetrahydrofuran ether glycol for 2 hours at the temperature of 100 ℃ and the vacuum degree of less than or equal to-0.08 Mpa;
pre-polymerization: cooling the dried mixture of the polycarbonate diol and the polytetrahydrofuran ether glycol to 70 ℃, adding 1.5 parts of HDI, 5 parts of IPDI and 0.01 part of organic bismuth catalyst, heating to 90 ℃ for reaction for 2 hours, controlling the-NCO content to reach a preset theoretical value, and cooling to 40 ℃ again; adding 0.15 part of 2, 2-dimethylolpropionic acid and acetone, uniformly stirring, heating to 75 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding 0.15 part of triethylamine, stirring for 10min for neutralization, then adjusting the rotating speed to high-speed stirring, adding 35 parts of deionized water, and then stirring at high speed for 15min for emulsification;
and (3) finished product: adding 0.6 part of isophorone diamine, reacting for 10min at the temperature of 35 ℃, and obtaining the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 90 wt% after vacuumizing and distilling to remove acetone; adding 1 wt% of hydroxyethyl cellulose, 0.8 wt% of polyether modified organosilicon wetting agent, 0.8 wt% of high molecular weight siloxane and 0.2 wt% of polyether modified organosilicon defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction waterborne polyurethane emulsion.
Test example 1: mechanical property test
The epoxy modified self-extinction aqueous polyurethane emulsions prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to mechanical property tests with reference to GB/T1040-2006, and the resulting elongation at break and strength at break are shown in Table 1:
TABLE 1 elongation at break and Strength at Break parameter Table
As shown in table 1, the emulsions obtained in examples 1 to 4 after being modified with epoxy resin and compounded with epoxy cross-linking agent in the prepolymerization stage have better elongation at break and breaking strength than the emulsions obtained in comparative example 1 without being modified with epoxy resin, comparative example 2 without being cross-linked with epoxy cross-linking agent, and comparative example 3 without being modified with epoxy group, and thus the emulsions obtained in this example have better strength and mechanical properties.
Test example 2: other Performance test
1. And (3) testing the granularity:
the emulsions of the emulsions prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to a particle size test using a malvern laser particle size tester, and the results of the test are shown in table 2.
2. Other performance tests:
using the emulsions prepared in examples 1 to 4 and comparative examples 1 to 3, the following tests were conducted, respectively, after scraping the film with a 30. + -. 5 μm film scraper and drying at 100 ℃ for 1min,
1) observing the appearance color of the adhesive films formed in the examples and the comparative examples, wherein the observation results are shown in Table 2;
2) cutting 5 sample strips in the longitude and latitude directions of the adhesive films formed in the embodiments and the comparative examples, testing the data of each sample strip by using a curvemeter, and weighing and averaging the results as shown in table 2;
3) after the adhesive films formed in the examples and the comparative examples are placed for 1 day, the surfaces of the adhesive films are wiped for 100 times by adopting 95% industrial ethanol, and whether the surfaces of the coatings have the phenomena of falling or brightening and the like is observed, and the results are shown in table 2;
4) the films formed in the examples and comparative examples were measured for gloss at 60 ℃ using a gloss meter, and the results are shown in table 2;
5) the adhesive films formed in the examples and comparative examples were scratched with fingernails, and the surface was observed for the occurrence of peeling or scratching, the results are shown in table 2;
6) the adhesive films formed in the examples and the comparative examples are weighed, the measured weight is recorded as M1, then the adhesive films are placed in deionized water for 1 day and taken out, the surface is wiped dry, the weight is recorded as M2, and the water absorption rate of each adhesive film is calculated by using the formula (M2-M1)/M1 and is shown in Table 2;
TABLE 2 other Performance parameter tables
As can be seen from Table 2, the particle sizes of the adhesive films formed in examples 1 to 4 were not significantly different from those of comparative examples 1 to 3, but the adhesive films formed in examples 1 to 4 were superior to those of the adhesive films formed in comparative examples 1 to 3 in the flex resistance, wet rub resistance, scratch resistance, water resistance and matting property.
According to the technical scheme of the embodiment, the epoxy modified self-extinction aqueous polyurethane emulsion is provided, epoxy resin is adopted for modification in a prepolymer stage, the epoxy resin enables a high molecular chain to be crosslinked in a reaction stage, and a rigid group on the epoxy group is introduced, so that the hardness of a system can be effectively improved, the hardness of polyurethane latex particles is improved, the stability of the latex particles is kept during film drying, and the glossiness cannot be greatly changed. In addition, in the process of drying and film forming of the polyurethane emulsion, the epoxy silane crosslinking agent is added during emulsion compounding, so that the molecular weight of the system is further improved, and the scratch resistance and the folding resistance of the adhesive film can be effectively improved; and the epoxy silane cross-linking agent is used in the single-component waterborne polyurethane, so that the storage stability is not negatively influenced.
While the invention has been described in conjunction with the specific embodiments set forth above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and scope of the appended claims.
Claims (15)
1. The epoxy modified self-extinction waterborne polyurethane emulsion is characterized by comprising the following components in percentage by weight: 85.5-96 wt% of epoxy modified self-extinction aqueous polyurethane dispersoid, 0.5-2 wt% of thickening agent, 2-5 wt% of cross-linking agent, 0.5-1 wt% of wetting agent, 0.5-1 wt% of hand feeling agent and 0.1-0.5 wt% of defoaming agent;
the epoxy modified self-extinction aqueous polyurethane dispersion comprises the following components in parts by weight:
10-20.5 parts of dihydric alcohol, 5.5-8.5 parts of diisocyanate, 0.002-0.04 part of catalyst, 0.08-0.4 part of hydrophilic chain extender, 0.01-0.2 part of epoxy resin, 0.1-0.2 part of neutralizer and 0.5-0.8 part of amine chain extender; wherein the R value before chain extension of the dispersion is 1.7-2, the amount of the hydrophilic chain extender accounts for 0.8-2% of the total mass of the dispersion, and the R value after chain extension of the dispersion is 1-1.2.
2. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the diol is one or a mixture of polycarbonate diol, polycaprolactone diol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate diol, poly 1, 4-butanediol adipate diol, and poly neopentyl glycol adipate 1, 6-hexanediol adipate diol.
3. The epoxy-modified self-extinction aqueous polyurethane emulsion of claim 1 wherein the diisocyanate is a mixture of one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4, 4-dicyclohexyl dimethylamine diisocyanate.
4. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the epoxy resin is a bisphenol a type epoxy resin or a multifunctional epoxy diluent.
5. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
6. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the amine chain extender is isophorone diamine, ethylene diamine or hydrazine hydrate.
7. The epoxy-modified self-extinction aqueous polyurethane emulsion of claim 1, wherein the catalyst is an organobismuth catalyst.
8. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the neutralizing agent is triethylamine or dimethylethanolamine.
9. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the thickener is one or more of hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyacrylic acid, polyacrylate, polyurethane, high molecular weight polyethylene oxide.
10. The epoxy-modified self-extinction aqueous polyurethane emulsion of claim 1, wherein the wetting agent is a polyether-modified silicone-based wetting agent.
11. The epoxy-modified self-matting aqueous polyurethane emulsion according to claim 1, wherein the defoaming agent is a polyether-modified silicone-based defoaming agent.
12. The epoxy-modified self-extinction aqueous polyurethane emulsion according to claim 1, wherein the cross-linking agent is any one of a carbodiimide cross-linking agent, aziridine, polyisocyanate, and epoxy silane.
13. The epoxy-modified self-extinction aqueous polyurethane emulsion of claim 1, wherein the handle agent is a silicone with a molecular weight of 1000-30000.
14. A preparation method of epoxy modified self-extinction waterborne polyurethane emulsion is characterized by comprising the following steps,
and (3) drying: drying a predetermined amount of dihydric alcohol under high temperature and vacuum conditions;
pre-polymerization: cooling the dried dihydric alcohol to 60-70 ℃, adding diisocyanate and a catalyst, heating to 80-100 ℃, reacting for 1-2h, controlling the-NCO content to reach a preset theoretical value, and cooling to 40-60 ℃ again; adding epoxy resin, a hydrophilic chain extender and acetone, uniformly stirring, heating to 75-85 ℃ for chain extension reaction, and cooling to below 40 ℃ after the content of the obtained-NCO reaches a preset theoretical value again to obtain a modified waterborne polyurethane prepolymer;
emulsification: adding a neutralizing agent, stirring for 10-20min for neutralization, then adjusting the rotating speed to high-speed stirring, adding metered deionized water, and stirring at high speed for 15 min;
and (3) finished product: adding amine chain extender, reacting at the temperature of 30-40 ℃ for 10-30 min, and removing acetone by vacuum distillation to obtain the epoxy modified self-extinction aqueous polyurethane dispersion with the solid content of 85.5-96 wt%; adding a predetermined amount of thickening agent, cross-linking agent, hand feeling agent and defoaming agent, stirring uniformly, and filtering to obtain the epoxy modified self-extinction aqueous polyurethane emulsion.
15. The method as claimed in claim 14, wherein the predetermined amount of the glycol is dried at 100 ℃ and 120 ℃ under a vacuum degree of-0.08 Mpa or less for 1 to 2 hours in the drying step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116135935A (en) * | 2023-02-20 | 2023-05-19 | 合肥工业大学 | High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof |
| CN116285457A (en) * | 2023-04-21 | 2023-06-23 | 广州市一化数字科技有限公司 | PU (polyurethane) sports terrace preparation method capable of improving molecular weight of chain extender |
| CN117965088A (en) * | 2024-02-20 | 2024-05-03 | 广东大自然家居科技研究有限公司 | Nanometer matt paint for wood floor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1512705A1 (en) * | 2003-09-02 | 2005-03-09 | C.O.I.M. S.p.A.- Chimica Organica Industriale Milanese | A process for the preparation of an aqueous dispersion of polyurethane resin having improved hydrolysis stability, and its use as an adhesive |
| CN101270221A (en) * | 2008-04-30 | 2008-09-24 | 武汉理工大学 | Method for preparing composite emulsion of epoxy resin-polyurethane |
| CN110407996A (en) * | 2019-09-16 | 2019-11-05 | 嘉兴学院 | One kind is from delustring aqueous polyurethane and preparation method thereof |
| CN111748072A (en) * | 2020-07-16 | 2020-10-09 | 安徽大学 | Water-based self-extinction surface treating agent for artificial or synthetic leather and preparation method thereof |
-
2022
- 2022-05-31 CN CN202210609243.XA patent/CN115058176A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1512705A1 (en) * | 2003-09-02 | 2005-03-09 | C.O.I.M. S.p.A.- Chimica Organica Industriale Milanese | A process for the preparation of an aqueous dispersion of polyurethane resin having improved hydrolysis stability, and its use as an adhesive |
| CN101270221A (en) * | 2008-04-30 | 2008-09-24 | 武汉理工大学 | Method for preparing composite emulsion of epoxy resin-polyurethane |
| CN110407996A (en) * | 2019-09-16 | 2019-11-05 | 嘉兴学院 | One kind is from delustring aqueous polyurethane and preparation method thereof |
| CN111748072A (en) * | 2020-07-16 | 2020-10-09 | 安徽大学 | Water-based self-extinction surface treating agent for artificial or synthetic leather and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨丽娟;李建军;彭晓宏;曹喜民;张雅胜;关仲翔;陈旭东;: "环氧改性高固含水性聚氨酯消光树脂的制备及性能研究" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116135935A (en) * | 2023-02-20 | 2023-05-19 | 合肥工业大学 | High-storage-stability room-temperature self-curing aqueous polyurethane for concrete protection and preparation method thereof |
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