CN108484864B - Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof - Google Patents
Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN108484864B CN108484864B CN201810348061.5A CN201810348061A CN108484864B CN 108484864 B CN108484864 B CN 108484864B CN 201810348061 A CN201810348061 A CN 201810348061A CN 108484864 B CN108484864 B CN 108484864B
- Authority
- CN
- China
- Prior art keywords
- organic sepiolite
- modified
- waterborne polyurethane
- organic
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
Abstract
The invention discloses organic sepiolite modified bi-component waterborne polyurethane and a preparation method thereof. The method comprises the steps of reacting oligomer polyol with diisocyanate under the action of a catalyst to obtain a polyurethane prepolymer, adding organic sepiolite to prepare an organic sepiolite modified waterborne polyurethane polyol dispersoid, and finally adding a defoaming agent, a leveling agent and a polyisocyanate curing agent to prepare the organic sepiolite modified bi-component waterborne polyurethane. The invention obviously improves the performances of the double-component waterborne polyurethane such as tensile modulus, tensile strength, storage modulus, loss modulus and the like, and the contact angle is as high as 97.7 degrees, the tensile modulus is as high as 388.2MPa, the tensile strength is as high as 69.2MPa, the storage modulus is as high as 1895.7MPa, and the loss modulus is as high as 173.8 MPa.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to organic sepiolite modified bi-component waterborne polyurethane and a preparation method thereof.
Background
The traditional coating mainly comprises solvent type polyurethane and solvent type double-component polyurethane, and the used organic solvent is inflammable, explosive, volatile and strong in smell, causes air pollution when in use and brings public nuisance problem. Meanwhile, the existing double-component polyurethane material generally contains TDI, MOCA, DOP, DBP, lead, mercury, tin catalysts and other toxic and harmful substances, and seriously harms the health of constructors and users.
With the increasing global awareness of environmental protection and the health of environmental regulations, the emission of Volatile Organic Compounds (VOCs) in traditional solvent-based coatings is increasingly restricted. The water paint uses water as dispersion medium, and has the advantages of non-inflammability, no toxicity, no environmental pollution, energy saving, etc. However, the currently used single-component polyurethanes have the disadvantages of poor water resistance, low viscosity, poor initial viscosity, high price and the like, (Paciss V G, et al. Waterborn polyurethane dispersions with a polycarbonate of a halogenated polyurethane as Coatings [ J ]. growth In organic Coatings, 2011,71 (2): 136:. 146). although the single-component polyurethane has the problem of water resistance, poor tensile modulus, tensile strength, storage modulus, loss modulus properties and the like, compared with the conventional solvent polyurethanes, the two-component waterborne polyurethanes have the problems of poor water resistance, poor tensile modulus, poor tensile strength, storage modulus, loss modulus properties and the like, (Dewhurst J E, Dry-Elder A S, Gao X P, et al. Property duration film formation of a thermoplastic polyurethane In the field of composite Coatings [ 12. application of C. 140. wax, D. C. 2001.790. application of composite Coatings [ 12. C.: 140. application of C. In. the fields of composite Coatings, the properties of two-component aqueous polyurethanes need to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides organic sepiolite modified bi-component waterborne polyurethane and a preparation method thereof. The organic sepiolite modified bi-component waterborne polyurethane has the advantages of more reasonable raw material formula, excellent performance, energy conservation and environmental protection, obviously improves the water resistance, tensile modulus, tensile strength, storage modulus, loss modulus and other properties of the bi-component waterborne polyurethane, and is beneficial to realizing the conversion of the bi-component waterborne polyurethane to the sustainable development direction.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
the preparation method of the organic sepiolite modified bi-component waterborne polyurethane comprises the following specific steps:
step 1, synthesizing an organic sepiolite modified aqueous polyurethane polyol dispersion: uniformly mixing oligomer polyol and diisocyanate, dropwise adding a catalyst, reacting for 2-3 hours at 85-90 ℃ to obtain a polyurethane prepolymer, adding organic sepiolite according to the mass ratio of gamma-aminopropyltriethoxysilane (KH-550) modified sepiolite (organic sepiolite) to the total mass of 3-6: 50, stirring for 2-3 hours, cooling to 55-65 ℃, adding the micromolecule hydrophilic chain extender, reacting for 1-2 hours, heating to 75-85 ℃, adding the micromolecule alcohol, reacting for 1-1.5 hours, adding an organic solvent to reduce the viscosity of the chain extender until the solution is colorless, reacting for 1-1.5 hours, adding the crosslinking agent, reacting for 1.5-2 hours, cooling to 15-25 ℃, adding the salt forming agent to perform neutralization reaction, neutralizing for 0.5-1 h, shearing, emulsifying, reacting for 0.5-1 h, and performing rotary evaporation to remove the organic solvent to obtain the organic sepiolite modified aqueous polyurethane polyol dispersion;
step 2, preparing the organic sepiolite modified bi-component waterborne polyurethane emulsion:
and adding a defoaming agent and a leveling agent into the organic sepiolite modified waterborne polyurethane polyol dispersoid, mixing with a polyisocyanate curing agent, and fully dispersing for 8-16 minutes to obtain the organic sepiolite modified bi-component waterborne polyurethane emulsion.
In the step 1, the mass fraction of each component in the total amount is as follows:
30-50% of oligomer polyol;
25-40% of diisocyanate;
0.1-0.4% of a catalyst;
4-8% of a small molecular alcohol chain extender;
2-6% of a small-molecule hydrophilic chain extender;
1-4% of a cross-linking agent;
2-6% of a salt forming agent;
in the step 1, the oligomer polyol is selected from one of polybutylene adipate diol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone triol and castor oil.
In the step 1, the polyisocyanate is selected from one or more of p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tetramethyl m-phenylene diisocyanate and 2-methylpentane diisocyanate.
In the step 1, the micromolecular hydrophilic chain extender is selected from one or two of dimethylolpropionic acid and dimethylolbutyric acid; the micromolecular hydrophilic chain extender is selected from one or more of spiroglycol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, butylethylpropanediol and neopentyl glycol; the cross-linking agent is selected from triethanolamine, pentaerythritol or glycerol; the salt forming agent is selected from one of triethylamine, sodium hydroxide and ammonia water.
In the step 1, the neutralization degree of the neutralization reaction is 100 percent, and the shearing speed is controlled at 2000 r/min.
In the step 2, the flatting agent is selected from a flatting agent with the model number of BYK-359 or BYK-361N; the defoaming agent is selected from defoaming agents with the models of BYK-070, BYK141 and BYK-A530; the component B is Bayer waterborne polyurethane curing agent Bayhydur XP 2547.
In the step 2, the organic sepiolite modified water-based polyurethane polyol dispersoid, the defoaming agent, the leveling agent and the polyisocyanate curing agent are mixed according to the weight ratio of 70-140: 0.1-1: 1-3; 4-10, and mixing uniformly to obtain the organic sepiolite modified bi-component waterborne polyurethane.
The invention also provides the organic sepiolite modified bi-component waterborne polyurethane prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
according to the invention, the organic sepiolite is used for modifying the bi-component waterborne polyurethane, so that the prepared organic sepiolite modified bi-component waterborne polyurethane emulsion has good water resistance, the tensile modulus, the tensile strength, the storage modulus, the loss modulus and other properties can be obviously improved, the contact angle is as high as 97.7 degrees, the tensile modulus is as high as 388.2MPa, the tensile strength is as high as 69.2MPa, the storage modulus is as high as 1895.7MPa, and the loss modulus is as high as 173.8 MPa.
Detailed Description
In order to better understand 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 described below, the organic sepiolite used was obtained from jingle chemical products ltd, beijing.
Comparative example 1: unmodified aqueous polyurethane emulsion
21.594g of poly (butylene adipate) diol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added, and the reaction is carried out for 3h, so that the polyurethane prepolymer is obtained. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, uniformly dispersing to obtain pure aqueous polyurethane dispersion, and performing rotary evaporation to remove acetone to obtain an emulsion, namely the unmodified aqueous polyurethane emulsion.
Preparation of film samples: casting the aqueous polyurethane emulsion into a film with the film thickness of about 1mm in a mould, naturally drying for 48h, placing the film in a vacuum oven, drying at 60 ℃ in vacuum to constant weight, taking out and placing the film in a dryer for later use.
TABLE 1 comparative example 1 film Performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 60.2 |
| Tensile modulus (25 ℃ C.) | MPa | 120.8 |
| Tensile Strength (25 ℃ C.) | MPa | 5.8 |
| Storage modulus (10 ℃ C.) | MPa | 1162.1 |
| Loss modulus (10 ℃ C.) | MPa | 55.1 |
Comparative example 2: organic sepiolite modified single-component waterborne polyurethane
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added to react for 3h to obtain a polyurethane prepolymer, and 5g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, uniformly dispersing to obtain an organic sepiolite-modified waterborne polyurethane dispersion liquid, and performing rotary evaporation to remove acetone to obtain an emulsion, namely the organic sepiolite-modified waterborne polyurethane emulsion.
Preparation of film samples: casting the organic sepiolite modified waterborne polyurethane emulsion into a film with the thickness of about 1mm in a mould, naturally drying for 48h, placing the film in a vacuum oven, drying the film in vacuum at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
TABLE 2 comparative example 2 film Performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 65.0 |
| Tensile modulus (25 ℃ C.) | MPa | 145.2 |
| Tensile Strength (25 ℃ C.) | MPa | 8.4 |
| Storage modulus (10 ℃ C.) | MPa | 1284.3 |
| Loss modulus (10 ℃ C.) | MPa | 59.3 |
Comparative example 3: unmodified two-component waterborne polyurethanes
(1) Synthesis of aqueous polyurethane polyol dispersion:
21.594g of poly (butylene adipate) diol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added, and the reaction is carried out for 3h, so that the polyurethane prepolymer is obtained. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and removing acetone by rotary evaporation to obtain the aqueous polyurethane polyol dispersoid.
(2) Preparing a two-component aqueous polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the unmodified two-component aqueous polyurethane emulsion.
Preparation of film samples: and (3) casting the double-component waterborne polyurethane emulsion into a film in a mold, wherein the film thickness is about 1mm, naturally drying for 48h, placing the film in a vacuum oven, drying the film in vacuum at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
TABLE 3 comparative example 3 film Performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 68.4 |
| Tensile modulus (25 ℃ C.) | MPa | 140.3 |
| Tensile Strength (25 ℃ C.) | MPa | 12.7 |
| Storage modulus (10 ℃ C.) | MPa | 1359.0 |
| Loss modulus (10 ℃ C.) | MPa | 60.1 |
Comparative example 4: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 1:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is added dropwise to react for 3h, a polyurethane prepolymer is obtained, and 1g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing the organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
TABLE 4 comparative example 4 film Performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 75.9 |
| Tensile modulus (25 ℃ C.) | MPa | 170.1 |
| Tensile Strength (25 ℃ C.) | MPa | 20.8 |
| Storage modulus (10 ℃ C.) | MPa | 1429.1 |
| Loss modulus (10 ℃ C.) | MPa | 65.7 |
Comparative example 5: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 11:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added to react for 3h to obtain a polyurethane prepolymer, and 11g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing the organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
TABLE 5 film Performance test results for comparative example 5
| Item | Unit of | Performance index |
| Contact angle | ° | 73.1 |
| Tensile modulus (25 ℃ C.) | MPa | 168.3 |
| Tensile Strength (25 ℃ C.) | MPa | 19.4 |
| Storage modulus (10 ℃ C.) | MPa | 1498.4 |
| Loss modulus (10 ℃ C.) | MPa | 68.4 |
Example 1: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 3:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is added dropwise to react for 3h, a polyurethane prepolymer is obtained, and 3g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing an organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
Table 6 example 1 film performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 90.3 |
| Tensile modulus (25 ℃ C.) | MPa | 369.1 |
| Tensile Strength (25 ℃ C.) | MPa | 69.2 |
| Storage modulus (10 ℃ C.) | MPa | 1840.3 |
| Loss modulus (10 ℃ C.) | MPa | 171.8 |
Example 2: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 5:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added to react for 3h to obtain a polyurethane prepolymer, and 5g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing an organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
Table 7 example 2 film performance test results
Example 3: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 7:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added to react for 3h to obtain a polyurethane prepolymer, and 7g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing an organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
Table 8 example 3 film performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 97.7 |
| Tensile modulus (25 ℃ C.) | MPa | 370.3 |
| Tensile Strength (25 ℃ C.) | MPa | 66.8 |
| Storage modulus (10 ℃ C.) | MPa | 1683.2 |
| Loss modulus (10 ℃ C.) | MPa | 168.4 |
Example 4: organic sepiolite modified two-component waterborne polyurethane (the mass ratio of the organic sepiolite to the total mass is 9:50)
(1) Synthesizing the organic sepiolite modified aqueous polyurethane polyol dispersoid:
21.594g of poly (butylene adipate) glycol with the molecular weight of 2000 is added into a 500mL four-neck flask, after drying for 1h at the temperature of 120 ℃ in vacuum, the temperature is reduced to 85 ℃, 10.162g of tetramethyl m-xylylene diisocyanate and 6.572g of naphthalene diisocyanate are added, 0.2g of dibutyltin dilaurate is dropwise added to react for 3h to obtain a polyurethane prepolymer, and 9g of organic sepiolite is added. Cooling to 60 ℃, adding 3g of dimethylolpropionic acid for reaction for 2h, heating to 75 ℃, adding 3.052g of diethylpentanediol for reaction for 1h, adding 15ml of acetone to reduce the viscosity of the reaction system until the solution is colorless, smoothly stirring, and continuing the reaction for 2 h. 2.48g of triethanolamine was added and reacted for 1.5 h. Cooling to 20 ℃, adding 3.14g of triethylamine to neutralize for 0.5h, adding 130g of deionized water to shear and emulsify for 0.5h, and performing rotary evaporation to remove acetone to obtain the organic sepiolite modified aqueous polyurethane polyol dispersoid.
(2) Preparing an organic sepiolite modified bi-component waterborne polyurethane emulsion: and (2) adding 1g of a leveling agent BYK-359 and 2g of a defoaming agent BYK-A530 into 110g of the prepared aqueous polyurethane polyol dispersoid, mixing with 5g of a curing agent Bayhydur XP2547, stirring for 15min, and uniformly mixing to obtain the organic sepiolite modified bi-component aqueous polyurethane emulsion.
Preparation of film samples: carrying out tape casting on the organic sepiolite modified bi-component waterborne polyurethane emulsion in a mold to form a film with the thickness of about 1mm, naturally drying for 48h, placing the film in a vacuum oven, carrying out vacuum drying at 60 ℃ to constant weight, taking out the film and placing the film in a dryer for later use.
TABLE 9 example 4 film Performance test results
| Item | Unit of | Performance index |
| Contact angle | ° | 92.1 |
| Tensile modulus (25 ℃ C.) | MPa | 385.3 |
| Tensile Strength (25 ℃ C.) | MPa | 62.7 |
| Storage modulus (10 ℃ C.) | MPa | 1786.2 |
| Loss modulus (10 ℃ C.) | MPa | 173.8 |
Analysis and comparison of test data listed in the table show that the organic sepiolite modified bi-component waterborne polyurethane is further compounded with a defoaming agent, a leveling agent and a curing agent for use to obtain the organic sepiolite modified bi-component waterborne polyurethane, the advantages are complementary, the problem that the performance of single waterborne polyurethane cannot completely meet the use requirement is solved, the contact angle of the prepared organic sepiolite modified bi-component waterborne polyurethane is up to 97.7 degrees, the tensile modulus is up to 388.2MPa, the tensile strength is up to 69.2MPa, the energy storage modulus is up to 1895.7MPa, and the loss modulus is up to 173.8 MPa.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
Claims (8)
1. The preparation method of the organic sepiolite modified bi-component waterborne polyurethane is characterized by comprising the following specific steps of:
step 1, synthesizing an organic sepiolite modified aqueous polyurethane polyol dispersion: uniformly mixing oligomer polyol and diisocyanate, dropwise adding a catalyst, reacting for 2-3 hours at 85-90 ℃ to obtain a polyurethane prepolymer, adding organic sepiolite according to the mass ratio of the organic sepiolite to the total amount of 3-6: 50 by taking the total mass of the oligomer polyol, the diisocyanate, the micromolecule hydrophilic chain extender, the micromolecule alcohol chain extender, the cross-linking agent and the salt forming agent as the total amount, stirring for 2-3 hours, cooling to 55-65 ℃, adding the micromolecule hydrophilic chain extender for reacting for 1-2 hours, heating to 75-85 ℃, adding the micromolecule alcohol chain extender, reacting for 1-1.5 hours, adding an organic solvent to reduce the viscosity until the solution is colorless, reacting for 1-1.5 hours, adding the cross-linking agent, reacting for 1.5-2 hours, cooling to 15-25 ℃, adding the salt forming agent for neutralizing, neutralizing for 0.5-1 hour, shearing and emulsifying, reacting for 0.5-1 hour, removing the organic solvent by rotary evaporation to obtain an organic sepiolite modified aqueous polyurethane polyol dispersion, wherein the organic sepiolite is modified sepiolite of KH-550;
step 2, preparing the organic sepiolite modified bi-component waterborne polyurethane emulsion:
and adding a defoaming agent and a leveling agent into the organic sepiolite modified waterborne polyurethane polyol dispersoid, mixing with a polyisocyanate curing agent, and fully dispersing for 8-16 minutes to obtain the organic sepiolite modified bi-component waterborne polyurethane emulsion.
2. The method according to claim 1, wherein in step 1, the oligomer polyol is one selected from the group consisting of polybutylene adipate diol, polytetrahydrofuran diol, polycarbonate diol, polycaprolactone triol, and castor oil.
3. The method according to claim 1, wherein in step 1, the polyisocyanate is one or more selected from the group consisting of p-phenylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tetramethylm-xylylene diisocyanate, and 2-methylpentane diisocyanate.
4. The preparation method according to claim 1, wherein in step 1, the small molecule hydrophilic chain extender is one or two selected from dimethylolpropionic acid and dimethylolbutyric acid; the chain extender of the small molecular alcohols is selected from one or more of spiroglycol, diethylpentanediol, trimethylpentanediol, ethylhexanediol, butylethylpropanediol and neopentyl glycol; the cross-linking agent is selected from triethanolamine, pentaerythritol or glycerol; the salt forming agent is selected from one of triethylamine, sodium hydroxide and ammonia water.
5. The method according to claim 1, wherein in step 1, the neutralization degree of the neutralization reaction is 100% and the shear rate is controlled to 2000 r/min.
6. The preparation method according to claim 1, wherein in the step 2, the leveling agent is selected from the leveling agents with the model number of BYK-359 or BYK-361N; the defoaming agent is selected from defoaming agents with the models of BYK-070, BYK141 and BYK-A530; the component B is Bayer waterborne polyurethane curing agent Bayhydur XP 2547.
7. The preparation method according to claim 1, wherein in the step 2, the organic sepiolite-modified aqueous polyurethane polyol dispersion, the defoaming agent, the leveling agent and the polyisocyanate curing agent are mixed in a weight ratio of 70-140: 1-3: 0.1-1: 4-10, and mixing uniformly to obtain the organic sepiolite modified bi-component waterborne polyurethane.
8. The organic sepiolite-modified two-component waterborne polyurethane prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810348061.5A CN108484864B (en) | 2018-04-18 | 2018-04-18 | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810348061.5A CN108484864B (en) | 2018-04-18 | 2018-04-18 | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484864A CN108484864A (en) | 2018-09-04 |
| CN108484864B true CN108484864B (en) | 2020-08-11 |
Family
ID=63312658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810348061.5A Active CN108484864B (en) | 2018-04-18 | 2018-04-18 | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484864B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1846473A1 (en) * | 2004-12-22 | 2007-10-24 | E.I. Dupont De Nemours And Company | Compositions of polyesters and sepiolite-type clays |
| CN102533085A (en) * | 2011-12-16 | 2012-07-04 | 展辰涂料集团股份有限公司 | Two-component polyurethane coating and preparation method thereof |
| CN102796238A (en) * | 2012-09-03 | 2012-11-28 | 武汉科技大学 | Sepiolite/polyurethane nanocomposite material and preparation method thereof |
| CN103554897A (en) * | 2013-10-25 | 2014-02-05 | 马鞍山科信咨询有限公司 | Hard polyurethane foaming plastic |
| CN105238004A (en) * | 2015-09-24 | 2016-01-13 | 安徽卓越电力设备有限公司 | Nonmetal corrosion-resistant prefabricated transformer substation box composite base plate |
| CN105273600A (en) * | 2014-07-03 | 2016-01-27 | 浙江省海洋开发研究院 | Preparation method of organosilicon-modified polyurethane hydrogel antifouling paint |
| CN105694625A (en) * | 2016-02-05 | 2016-06-22 | 南京锎巴新材料科技有限公司 | Exterior wall waterproofing heat-insulating decorating integrated material and preparation method thereof |
| CN106459337A (en) * | 2014-06-24 | 2017-02-22 | 比克化学股份有限公司 | Polyurethane two-component or multi-component systems having a latent thickening tendency |
| CN106750086A (en) * | 2016-12-14 | 2017-05-31 | 浙江吉高新材料有限公司 | A kind of high-performance reaction injection molding polyurethane and preparation method thereof |
| CN107163209A (en) * | 2017-07-18 | 2017-09-15 | 合肥万之景门窗有限公司 | A kind of hard polyaminoester external wall flame-retarding heat-preserving material and preparation method thereof |
| CN107892868A (en) * | 2017-11-03 | 2018-04-10 | 洛阳双瑞防腐工程技术有限公司 | A kind of double-composition polyurethane waterproof paint and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180043656A1 (en) * | 2017-09-18 | 2018-02-15 | LiSo Plastics, L.L.C. | Oriented Multilayer Porous Film |
-
2018
- 2018-04-18 CN CN201810348061.5A patent/CN108484864B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1846473A1 (en) * | 2004-12-22 | 2007-10-24 | E.I. Dupont De Nemours And Company | Compositions of polyesters and sepiolite-type clays |
| CN102533085A (en) * | 2011-12-16 | 2012-07-04 | 展辰涂料集团股份有限公司 | Two-component polyurethane coating and preparation method thereof |
| CN102796238A (en) * | 2012-09-03 | 2012-11-28 | 武汉科技大学 | Sepiolite/polyurethane nanocomposite material and preparation method thereof |
| CN103554897A (en) * | 2013-10-25 | 2014-02-05 | 马鞍山科信咨询有限公司 | Hard polyurethane foaming plastic |
| CN106459337A (en) * | 2014-06-24 | 2017-02-22 | 比克化学股份有限公司 | Polyurethane two-component or multi-component systems having a latent thickening tendency |
| CN105273600A (en) * | 2014-07-03 | 2016-01-27 | 浙江省海洋开发研究院 | Preparation method of organosilicon-modified polyurethane hydrogel antifouling paint |
| CN105238004A (en) * | 2015-09-24 | 2016-01-13 | 安徽卓越电力设备有限公司 | Nonmetal corrosion-resistant prefabricated transformer substation box composite base plate |
| CN105694625A (en) * | 2016-02-05 | 2016-06-22 | 南京锎巴新材料科技有限公司 | Exterior wall waterproofing heat-insulating decorating integrated material and preparation method thereof |
| CN106750086A (en) * | 2016-12-14 | 2017-05-31 | 浙江吉高新材料有限公司 | A kind of high-performance reaction injection molding polyurethane and preparation method thereof |
| CN107163209A (en) * | 2017-07-18 | 2017-09-15 | 合肥万之景门窗有限公司 | A kind of hard polyaminoester external wall flame-retarding heat-preserving material and preparation method thereof |
| CN107892868A (en) * | 2017-11-03 | 2018-04-10 | 洛阳双瑞防腐工程技术有限公司 | A kind of double-composition polyurethane waterproof paint and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Characterization and properties of sepiolite/polyurethane nanocomposites;Hongxiang Chen;《Materials Science and Engineerin》;20070315;第445卷;第725-730页 * |
| Study on thermal properties of polyurethane nanocomposites based on organosepiolite;Hongxiang Chen;《Polymer Degradation and Stability》;20120103;第97卷(第3期);第242-247页 * |
| 凹凸棒石粘土在双组分聚氨酯涂料中的应用;金叶玲;《应用化工》;20051031;第34卷(第10期);第601-603页 * |
| 软段长度对聚氨酯/海泡石复合材料结构及性能的影响;余桂辉;《高分子材料科学与工程》;20151231;第31卷(第12期);第67-72页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484864A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101225226B (en) | Method for preparing water-dispersion montmorillonite/organic block polyurethane nano composite material and uses thereof | |
| JP5452794B2 (en) | Aqueous polyurethane resin emulsion coating composition and method for producing the same | |
| CN112457462B (en) | Nonionic waterborne polyurethane and preparation method and application thereof | |
| CN102827340A (en) | Organosilicon-modified waterborne polyurethane composite material and applications thereof | |
| CN111793188A (en) | Hydroxyl-containing self-extinction waterborne polyurethane and high-performance self-extinction coating composed of same | |
| CN108034349B (en) | Preparation method of octanitrosilsesquioxane modified bi-component waterborne polyurethane emulsion | |
| CN109535372B (en) | Waterborne polyurethane and preparation method thereof | |
| EP3265495A1 (en) | Polybutadienols for producing glassy polyurethanes | |
| KR101649759B1 (en) | Manufacturing method of waterborne polyurethane using epoxy resin | |
| CN108484864B (en) | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof | |
| CN108239457B (en) | Water-based peelable glue, and preparation method and application thereof | |
| CN104592469B (en) | Anionic polyurethane aqueous dispersion, its prepolymer monomer and preparation technology | |
| CN112778493B (en) | Polypropylene carbonate polyol type water-based polyurethane waterproof emulsion and preparation method and application thereof | |
| CN109942792A (en) | A kind of phosphorous water-based polyurethane curing agent and its preparation method and application | |
| EP0006204B1 (en) | Aqueous dispersions of oligomeric or polymeric plastics, a process for preparing same and their use | |
| CN109651582B (en) | Waterborne polyurethane ink binder and preparation method thereof | |
| CN110358046A (en) | A kind of heatproof transfer coatings aqueous polyurethane emulsion of good film-forming property and preparation method thereof | |
| CN114716643B (en) | Preparation method of sulfonic acid type waterborne polyurethane adhesive | |
| JP3197130B2 (en) | Thermocrosslinkable polyurethane emulsion composition | |
| TWI667264B (en) | Sulfonic acid based aqueous polyurethane emulsion and process of producing the same | |
| CN109503800A (en) | A kind of modified aqueous polyurethane and preparation method thereof | |
| AU2020103155A4 (en) | Non-ionic water based polyurethane and preparation method and use thereof | |
| CN104211898A (en) | Amino-terminated aqueous polyurethane dispersion and preparation method thereof | |
| EP1765899A1 (en) | Method for producing amino-functional polyurethane prepolymers | |
| CN112538152B (en) | Waterborne polyurethane-polyurea dispersion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |