CN107892868A - A kind of double-composition polyurethane waterproof paint and preparation method thereof - Google Patents
A kind of double-composition polyurethane waterproof paint and preparation method thereof Download PDFInfo
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- CN107892868A CN107892868A CN201711069395.0A CN201711069395A CN107892868A CN 107892868 A CN107892868 A CN 107892868A CN 201711069395 A CN201711069395 A CN 201711069395A CN 107892868 A CN107892868 A CN 107892868A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of double-composition polyurethane waterproof paint, by first component and second component according to 1:1 1.5 mass ratio is mixed；In terms of mass fraction, first component is mainly made up of following raw material：40 100 parts of PPG, 30 60 parts of isocyanates, 0.7 8 parts of modifying agent；In terms of mass fraction, second component is mainly made up of following raw material：15 20 parts of water, 0.5 1 parts of dispersant, 0.5 2 parts of antioxidant, CO20.1 1 parts of absorbent, 3 10 parts of plasticizer, 0.1 1 parts of levelling agent, 30 55 parts of filler, 0.1 1.5 parts of defoamer.The polyurethane water-proof paint of the present invention, no added organic solvent is environmentally safe, harmless to the personnel health such as produce, construct；Possess excellent tensile strength, elongation at break, tearing strength, low temperature flexibility and heat resistance；Paint film is influenceed small, energy rapid curing by ambient humidity, and workability is good.
Description
Technical field
The present invention relates to building water-proof paint technical field, and in particular to a kind of double-composition polyurethane waterproof paint and its system
Preparation Method.
Background technology
Polyurethane water-proof paint have film elastic height, good-extensibility, chemical-resistant is good, heat-resisting ageing-resisting performance is good,
The features such as adhesive property is excellent, easy for construction, is widely used in building waterproofing industry.Existing polyurethane water-proof paint is polymerizeing
With lead class or tin catalyst would generally be used in solidification process, the harmful components of these catalyst, which are readily diffused into water, to threaten
Health.
The application for a patent for invention specification of Application No. 2016112237375 discloses a kind of uncured polyurethane water-proof and applied
Material and preparation method thereof, body of paste state is remained after the product construction of the invention, there is superior durability, endurance
Property, resistant of high or low temperature and extensibility, and adhesive property is good, self-healing performance is good, but it is unsuitable for the performances such as intensity, elongation at break
It is required that higher buildings waterproof field.
The application for a patent for invention specification of Application No. 2008101826973 discloses a kind of dual-component polyurethane waterproof and applied
Material, blocked using a variety of polyether resin compounding uses, and using amine terminated polyether resin, polymerization process be controlled,
The component A of function admirable is made, by adding vulcanizing agent in B component, carries out vulcanization intensified response, substantially increases B component
Intensity, the coating has the advantages of high solid, high intensity, high elongation at tear, but tenderness is low, heat resistance is bad,
And toluene di-isocyanate(TDI) volatility is had a great influence by vapour pressure in component A.
The content of the invention
It is an object of the invention to provide a kind of environment-friendly type, high intensity, high elongation at tear, low temperature flexibility is good, heat resistance is good,
Good double-composition polyurethane waterproof paint of film high specific surface area, workability and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted in the present invention is：A kind of double-composition polyurethane waterproof paint,
By first component and second component according to 1:1-1.5 mass ratio be mixed；
In terms of mass fraction, first component is mainly made up of following raw material：PPG 40-100 parts, isocyanates 30-60 parts,
Modifying agent 0.7-8 parts；
In terms of mass fraction, second component is mainly made up of following raw material：Water 15-20 parts, dispersant 0.5-1 parts, antioxidant 0.5-2
Part, CO2Absorbent 0.1-1 parts, plasticizer 3-10 parts, levelling agent 0.1-1 parts, filler 30-55 parts, defoamer 0.1-1.5 parts.
Preferably, described PPG select polyether Glycols and polyether-tribasic alcohol simultaneously, and polyether Glycols and
The mass ratio of polyether-tribasic alcohol is 0.8-2:1.
Preferably, described isocyanates is methyl diphenylene diisocyanate.
Preferably, described modifying agent selects organo montmorillonite and waterglass simultaneously, and organo montmorillonite and waterglass
Mass ratio is 0.8-1.2:1.
Preferably, it is used to adjust the polyurethane water-proof paint also including 0.2-1 mass fractions in the raw material of second component
To the pigment of grey；Further preferably, described pigment is simultaneously from carbon black and middle Huang and selected from phthalocyanine blue and iron oxide red
In one kind.
Preferably, described dispersant is selected from least one of BASF-4585, SN-5040 and MOK-5036；Described is anti-
Oxygen agent is selected from least one of TDS-115, JY-1076 and JY-1135；Described CO2Absorbent is calcium hydroxide；Described
Plasticizer is S-5408；Described levelling agent is selected from least one of AMS-2020, BYK-345 and RM-2020.
Preferably, described filler is from talcum powder and in kaolin, powdered whiting and precipitated calcium carbonate
One kind, and talcum powder and the latter's mass ratio are 2-3:1.
Preferably, described defoamer is A10.
A kind of preparation method of double-composition polyurethane waterproof paint, comprises the following steps：
Step 1: first component and second component are prepared respectively（Without sequencing, first prepare first component or first prepare second component）：
The preparation method of first component is：Mass fraction weighs the raw material of first component as described above；PPG is added
Into closed reaction vessel, 100-120 DEG C is warming up under stirring condition, relative degree of vacuum is that below -0.095MPa is dehydrated,
A length of 1-2h, is cooled to 60-80 DEG C during dehydration；Isocyanates and modifying agent are added, 75-85 DEG C is warming up under stirring condition, is protected
Temperature to-NCO content reaches 6%-9%（- NCO accounts for the mass fraction of first component）, room temperature is cooled to, that is, first component is made；
The preparation method of second component is：Mass fraction weighs the raw material of second component as described above；Water and dispersant are added
In reaction vessel, 12-18 minutes are disperseed under 500-900r/min rotating speed；Add antioxidant, CO2Absorbent, plasticizer, levelling
Agent and filler, if also including pigment in the raw material of second component, pigment also adds at this moment, is mixed under 500-900r/min rotating speed
Close uniform；Defoamer is added, disperses 7-13 minutes under 600-800r/min rotating speed；Fineness is ground to as less than 40 μm, that is, is made
Obtain second component；
Step 2: first component and second component is each kept separately first component and second component before use according to 1:1-1.5 matter
Double-composition polyurethane waterproof paint is made than well mixed in amount.
Beneficial effect and the mechanism of action：
1st, polyurethane water-proof paint of the invention, no added organic solvent is environmentally safe, and to producing, constructing etc., personnel are good for
Health is harmless；Possess excellent tensile strength, elongation at break, tearing strength, low temperature flexibility and heat resistance；Paint film is by ambient humidity
Small, energy rapid curing is influenceed, workability is good；
2nd, first component uses PPG and isocyanates synthesis of polyurethane in the present invention, and polyurethane is participated in using modifying agent
Synthetic reaction, introduced in polyurethane structural and strengthen key, strengthen coating intensity；Polyether Glycols contain with polyether-tribasic alcohol primary hydroxyl
Measure of a relatively high, and there is high relative molecular mass, the polyurethane structural relative compact synthesized with isocyanates, coating is prevented
Water-based energy is significant；Isocyanates is methyl diphenylene diisocyanate, and its vapour pressure is relatively small, caused volatilization
Gas is few, stable performance；Modifying agent uses organo montmorillonite and waterglass, the lamella and polyurethane matrix of organo montmorillonite simultaneously
Between strong interaction can limit the slip of polyurethane chain, and then the heat endurance of raising polyurethane water-proof paint, in addition
The lamella of organo montmorillonite can also play heat insulating function as heat insulation layer；Waterglass can be hydrolyzed to the silanol chemical combination of activity
Thing, silicon alcohol compound react with isocyanates, so as to introduce the silica structure of excellent performance in polyurethane structural, due to Si-O
Key is more more stable than C-C, C-N and C-O key, therefore film can be made to have higher heat resistance, chemicals-resistant, weatherability and tension
Intensity；
3rd, pigment is added in second component, can makes polyurethane water-proof paint that there is certain color, be easy to construct；Pigment is selected
Three kinds of pigment, i.e. carbon black and middle yellow and one kind in iron oxide red and phthalocyanine blue, can make the polyurethane water-proof paint be in
Grey, it is not only convenient for constructing, and the ageing-resistant performance of polyurethane water-proof paint can be increased, increases service life；Plasticizer
S-5408 is silicon cave modifying composition, can improve suppleness, glossiness, levelability and the scratch resistance of paint film；Defoamer A10 is
Molecular level defoams material, and defaoming mechanisms are special, and the defoamer also has the wetting action not available for traditional defoamer.
Embodiment
With reference to specific embodiment, the present invention will be further described in detail.
Embodiment 1
A kind of composite modified double-composition polyurethane waterproof paint, by first component and second component according to 1:1.5 mass ratio mixing system
Into；Wherein first component and second component is made up of following raw material respectively：
First component：Polyether Glycols 40kg, polyether-tribasic alcohol 45kg, methyl diphenylene diisocyanate 30kg, organo montmorillonite
1.725kg waterglass 1.725kg；
Second component：Water 15kg；Dispersant（BASF-4585）0.5kg, antioxidant（TDS-115）0.5kg, CO2Absorbent（Hydrogen-oxygen
Change calcium）0.3kg, plasticizer（S-5408）3kg, levelling agent（AMS-2020）0.2kg, filler 30kg（Wherein talcum powder 20kg, again
Matter calcium carbonate 10kg）, pigment 0.2kg（Wherein carbon black 0.06kg, phthalocyanine blue 0.02kg, middle yellow 0.12kg）, defoamer（A10）
0.3kg；
The preparation method of the double-composition polyurethane waterproof paint, comprises the following steps：
Step 1: first component and second component are prepared respectively：
The preparation method of first component：The raw material of first component is weighed according to the mass fraction；By polyether Glycols and polyethers ternary
Alcohol is added to reactor（Closed reaction vessel）In, 110 DEG C are warming up under stirring condition, vacuumizes and is decompressed to relative degree of vacuum
To be dehydrated below -0.095MPa, a length of 1h during dehydration, 70 DEG C are cooled to；Add methyl diphenylene diisocyanate, organic
Montmorillonite and waterglass, are warming up to 85 DEG C under stirring condition, and insulation to-NCO content reaches 6%-9%（About 3h）, room temperature is cooled to, i.e.,
First component is made；
The preparation method of second component：The raw material of second component is weighed according to the mass fraction；Water and dispersant are added into reactor
In, disperse 15 minutes under 900r/min rotating speed；Add antioxidant, CO2Absorbent, plasticizer, levelling agent, filler and pigment,
It is well mixed under 800r/min rotating speed（About 2h）；Defoamer is added, is disperseed 10 minutes under 600r/min rotating speed；Using horizontal
Grinder is ground to fineness as less than 40 μm, that is, second component is made；
Step 2: first component and second component is each kept separately first component and second component before use according to described quality
Than well mixed, that is, double-composition polyurethane waterproof paint is made；
Obtained coating gray, coating the key technical indexes are shown in Table 1.
Embodiment 2
A kind of composite modified double-composition polyurethane waterproof paint, by first component and second component according to 1:1.2 mass ratio mixing system
Into wherein first component and second component is made up of following raw material respectively：
First component：Polyether Glycols 45kg, polyether-tribasic alcohol 40kg, methyl diphenylene diisocyanate 50kg, organo montmorillonite
2.025kg waterglass 2.025kg；
Second component：Water 19kg；Dispersant（SN-5040）0.8kg, antioxidant（JY-1076）1.5kg, CO2Absorbent（Hydroxide
Calcium）0.8kg, plasticizer（S-5408）9kg, levelling agent（BYK-345）0.5kg, filler 50kg（Wherein talcum powder 35kg, lightweight
Calcium carbonate 15kg）, pigment 0.6kg（Wherein carbon black 0.20kg, iron oxide red 0.08kg, middle yellow 0.32kg）, defoamer（A10）
1.0kg；
Preparation method is the same as embodiment 1；Obtained coating gray, coating the key technical indexes are shown in Table 1.
Embodiment 3
A kind of composite modified double-composition polyurethane waterproof paint, by first component and second component according to 1:1.2 mass ratio mixing system
Into wherein first component and second component is made up of following raw material respectively：
First component：Polyether Glycols 50kg, polyether-tribasic alcohol 50kg, methyl diphenylene diisocyanate 60kg, organo montmorillonite
2.4kg, waterglass 2.4kg；
Second component：Water 17kg；Dispersant（BASF-4585）0.6kg, antioxidant（JY-1135）1.0kg, CO2Absorbent（Hydrogen-oxygen
Change calcium）0.7kg, plasticizer（S-5408）8kg, levelling agent（BYK-345）0.4kg, filler 45kg（It is wherein talcum powder 30kg, light
Matter calcium carbonate 15kg）, pigment 0.7kg（Wherein carbon black 0.20kg, phthalocyanine blue 0.10kg, middle yellow 0.40kg）, defoamer（A10）
0.8kg；
Preparation method is the same as embodiment 1；Obtained coating gray, coating the key technical indexes are shown in Table 1.
Embodiment 4
A kind of composite modified double-composition polyurethane waterproof paint, by first component and second component according to 1:1 mass ratio is mixed,
Wherein first component and second component is made up of following raw material respectively：
First component：Polyether Glycols 55kg, polyether-tribasic alcohol 30kg, methyl diphenylene diisocyanate 45kg, organo montmorillonite
1.95kg, waterglass 1.95kg；
Second component：Water 20kg；Dispersant（MOK-5036）1.0kg, antioxidant（JY-1135）2kg, CO2Absorbent（Hydroxide
Calcium）0.9kg, plasticizer（S-5408）10kg, levelling agent（RM-2020）0.7kg, filler 55kg（Wherein talcum powder 40kg, kaolinite
Native 15kg）, pigment 0.8kg（Wherein carbon black 0.25kg, iron oxide red 0.10kg, middle yellow 0.45kg）, defoamer（A10）1.3kg；
Preparation method is the same as embodiment 1；Obtained coating gray, coating the key technical indexes are shown in Table 1.
The film that thickness is 1.5mm ± 0.2mm is respectively prepared in embodiment 1-4 water-repellent paint, by GB/T19250-
2013《Polyurethane water-proof paint》Performance test is carried out, test result is as follows：
The obtained polyurethane water-proof paint of the present invention shows excellent comprehensive it can be seen from the performance indications and assay of table 1
Close the index such as performance, its tensile strength, elongation at break, tearing strength and be satisfied by requirements of the GB/T19250-2013 to product.
In addition, the present invention water-repellent paint non-volatility organic solvent, workability is good, low temperature flexibility is good, heat resistance is good, film is every
High specific surface area.
Above example is only presently preferred embodiments of the present invention, any improvement or replacement for not departing from basic idea of the present invention
Protection scope of the present invention all should be included.
Claims (10)
- A kind of 1. double-composition polyurethane waterproof paint, it is characterised in that：By first component and second component according to 1:1-1.5 mass ratio It is mixed；In terms of mass fraction, first component is mainly made up of following raw material：PPG 40-100 parts, isocyanates 30-60 parts, Modifying agent 0.7-8 parts；In terms of mass fraction, second component is mainly made up of following raw material：Water 15-20 parts, dispersant 0.5-1 parts, antioxidant 0.5-2 Part, CO2Absorbent 0.1-1 parts, plasticizer 3-10 parts, levelling agent 0.1-1 parts, filler 30-55 parts, defoamer 0.1-1.5 parts.
- A kind of 2. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described PPG is same Shi Xuanyong polyether Glycols and polyether-tribasic alcohol, and the mass ratio of polyether Glycols and polyether-tribasic alcohol is 0.8-2:1.
- A kind of 3. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described isocyanates is two Methylenebis phenyl isocyanate.
- A kind of 4. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described modifying agent selects simultaneously With organo montmorillonite and waterglass, and the mass ratio of organo montmorillonite and waterglass is 0.8-1.2:1.
- A kind of 5. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Also wrapped in the raw material of second component Include the pigment for being used to the polyurethane water-proof paint being adjusted to grey of 0.2-1 mass fractions.
- A kind of 6. double-composition polyurethane waterproof paint as claimed in claim 5, it is characterised in that：Described pigment is selected simultaneously Carbon black and middle yellow and one kind in phthalocyanine blue and iron oxide red.
- A kind of 7. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described dispersant is selected from At least one of BASF-4585, SN-5040 and MOK-5036；Described antioxidant is selected from TDS-115, JY-1076 and JY- At least one of 1135；Described CO2Absorbent is calcium hydroxide；Described plasticizer is S-5408；Described levelling agent Selected from least one of AMS-2020, BYK-345 and RM-2020.
- A kind of 8. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described filler selects talcum Powder and one kind in kaolin, powdered whiting and precipitated calcium carbonate, and talcum powder and the latter's mass ratio are 2-3:1.
- A kind of 9. double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that：Described defoamer is A10.
- 10. a kind of preparation method of double-composition polyurethane waterproof paint as claimed in claim 1, it is characterised in that including following Step：Step 1: first component and second component are prepared respectively：The preparation method of first component is：The raw material of first component is weighed according to mass fraction described in claim 1；By PPG It is added in closed reaction vessel, 100-120 DEG C is warming up under stirring condition, relative degree of vacuum is that below -0.095MPa is carried out Dehydration, a length of 1-2h during dehydration, is cooled to 60-80 DEG C；Isocyanates and modifying agent are added, 75-85 is warming up under stirring condition DEG C, it is incubated extremely-NCO content and reaches 6%-9%, be cooled to room temperature, that is, first component is made；The preparation method of second component is：The raw material of second component is weighed according to mass fraction described in claim 1；By water and dispersant Add in reaction vessel, 12-18 minutes are disperseed under 500-900r/min rotating speed；Add antioxidant, CO2Absorbent, plasticizer, Levelling agent and filler, if also including pigment in the raw material of second component, pigment also adds at this moment, 500-900r/min rotating speed It is lower well mixed；Defoamer is added, disperses 7-13 minutes under 600-800r/min rotating speed；Fineness is ground to as less than 40 μm, Second component is made；Step 2: first component and second component is each kept separately first component and second component before use according to claim 1 institute The mass ratio stated is well mixed, that is, double-composition polyurethane waterproof paint is made.
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| CN108484864A (en) * | 2018-04-18 | 2018-09-04 | 南京理工大学 | Modified bi-component aqueous polyurethane of organic sepiolite and preparation method thereof |
| CN110423550A (en) * | 2019-09-16 | 2019-11-08 | 巩义市弘盛管道设备有限公司 | A kind of antibacterial mould-proof-type water cure polyurethane building water-repellent paint and preparation method thereof |
| CN110452611A (en) * | 2019-08-26 | 2019-11-15 | 武汉比邻科技发展有限公司 | A kind of nano modified polyurethane water-repellent paint and preparation method thereof |
| WO2024113518A1 (en) * | 2022-12-02 | 2024-06-06 | 龙牌涂料(北京)有限公司 | Waterborne polyurethane emulsion and preparation method therefor |
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| CN108484864B (en) * | 2018-04-18 | 2020-08-11 | 南京理工大学 | Organic sepiolite modified bi-component waterborne polyurethane and preparation method thereof |
| CN110452611A (en) * | 2019-08-26 | 2019-11-15 | 武汉比邻科技发展有限公司 | A kind of nano modified polyurethane water-repellent paint and preparation method thereof |
| CN110423550A (en) * | 2019-09-16 | 2019-11-08 | 巩义市弘盛管道设备有限公司 | A kind of antibacterial mould-proof-type water cure polyurethane building water-repellent paint and preparation method thereof |
| WO2024113518A1 (en) * | 2022-12-02 | 2024-06-06 | 龙牌涂料(北京)有限公司 | Waterborne polyurethane emulsion and preparation method therefor |
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