CN108949002B - Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances - Google Patents

Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances Download PDF

Info

Publication number
CN108949002B
CN108949002B CN201810881113.5A CN201810881113A CN108949002B CN 108949002 B CN108949002 B CN 108949002B CN 201810881113 A CN201810881113 A CN 201810881113A CN 108949002 B CN108949002 B CN 108949002B
Authority
CN
China
Prior art keywords
graphene sheet
reacting
light
stirring
graphene
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
Application number
CN201810881113.5A
Other languages
Chinese (zh)
Other versions
CN108949002A (en
Inventor
段宝荣
翟智宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Jiajia smart home Co., Ltd
Original Assignee
Zhejiang Jiajia Smart Home Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Jiajia Smart Home Co ltd filed Critical Zhejiang Jiajia Smart Home Co ltd
Priority to CN201810881113.5A priority Critical patent/CN108949002B/en
Publication of CN108949002A publication Critical patent/CN108949002A/en
Application granted granted Critical
Publication of CN108949002B publication Critical patent/CN108949002B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a preparation method of a flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances, wherein 0.6g of catalyst in the step (1), 80g of polytetrahydrofuran ether glycol and 40g of isophorone diisocyanate are mixed in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condenser, the mixture is reacted for 1h at 70 ℃, 0.2g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3) are added, the reaction time is 2h, the reaction temperature is 80 ℃, and a polyurethane prepolymer A is obtained; 1.2g of aminobenzenesulfonic acid and 20g of acetone are added into the prepolymer A, the mixture is reacted for 2 hours at the temperature of 75 ℃, 1g of 2,4, 6-trihydroxybenzoic acid and 1.2g of the light-resistant agent in the step (2) are added, the reaction temperature is 85 ℃, the reaction time is 0.5 hour, 12g of triethylamine is added for neutralization reaction for 30 minutes, 110g of water is added, and the mixture is stirred and emulsified to obtain the flame-retardant and light-resistant waterborne polyurethane coating.

Description

Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances
This application is a divisional application of the patent application with application number 201610775497.3.
Technical Field
The invention relates to a preparation method of a waterborne polyurethane coating, in particular to furniture or metal appliances prepared by the preparation method of a graphene modified flame-retardant and light-resistant waterborne polyurethane coating.
Background
The polyurethane is mainly applied to the fields of leather finishing, textile printing and dyeing, paper making industry, building coating, adhesives and the like. Because the paint and the paint sprayed on the surfaces of inner and outer walls, furniture or metal appliances are in direct or indirect contact with human beings, the toxic and harmful paint threatens the health of people at all times. In addition, the field of use is always in contact with sunlight, the sunlight contains a large amount of ultraviolet light harmful to colored objects, the wavelength of the ultraviolet light is about 290-460 nm, and the harmful ultraviolet light causes the color of the coating to change through the chemical oxidation-reduction action.
Dibutyltin dilaurate is usually used as a catalyst for polyurethane polymerization, but because heavy metal tin causes harm to the environment along with the degradation of polyurethane, the harm degree of polyurethane coating residues to the environment is reduced, which has become a technical problem.
In order to improve the light resistance of polyurethane resin, a mode of adding an ultraviolet absorbent and an antioxidant is often adopted, but the traditional synthetic antioxidants such as tert-butyl hydroxy anisole, tert-butyl hydroperoxide, tert-butyl hydroquinone and the like have larger toxic and side effects and carcinogenicity, while the traditional method of adding organosilicon materials to improve the water resistance is not satisfactory, so that more efficient and environment-friendly water resistance and light resistance measures need to be found.
Like most other high molecular materials, polyurethane is not heat-resistant, is easy to ignite, generates toxic gas and harms personal and property safety. The polyurethane product has certain flame retardance, the flame retardant is the most common method, and the flame retardant which is often added at present is phosphate and halogenated phosphate, and the flame retardant is not ideal for improving the flame retardance of the polyurethane.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of graphene modified flame-retardant and light-resistant waterborne polyurethane coating, wherein the waterborne polyurethane coating is modified by graphene, and a self-made catalyst, a light-resistant agent and a flame retardant are selected to improve the flame retardance and the light resistance of the waterborne polyurethane and reduce the toxicity of the polyurethane.
1. The preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized by comprising the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst, wherein the yield is 70%;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.05g of graphene sheet into 400mL of concentrated sulfuric acid, 0.4g of 4-triphenylamine borate and 0.3g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with the ultrasonic power of 500W and the ultrasonic frequency of 100KHz, diluting with 450mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 8h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.)%, and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of catalyst in the step (1), 80g of polytetrahydrofuran ether glycol and 40g of isophorone diisocyanate in a 500ml four-neck flask with a stirring paddle, a thermometer and a condensation tube, reacting for 1h at 70 ℃, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) 1.2g of aminobenzenesulfonic acid and 20g of acetone are added into the prepolymer A, the mixture is reacted for 2 hours at the temperature of 75 ℃, 1g of 2,4, 6-trihydroxybenzoic acid and 1.2g of the light-resistant agent in the step (2) are added, the reaction temperature is 85 ℃, the reaction time is 0.5 hour, 12g of triethylamine is added for neutralization reaction for 30 minutes, 110g of water is added, and the mixture is stirred and emulsified to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
2. The preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized by comprising the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.6g of sodium carboxymethylcellulose, 1.8g of titanium trichloride, 0.6g of magnesium ethoxide, 5.4g of zinc acetate, 4.6g of diethanolamine and 3.5g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst, wherein the yield is 70%;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.8g of sodium tripolyphosphate, 6.2g of citric acid, 4.8g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 2h, adding 4.2g of aluminum carbonate and 1.8g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.6g of dimethylformamide, and stirring at 80 ℃ for 2h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.4g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 90 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with the ultrasonic power of 500W and the ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with the deionized water until the deionized water is neutral, finally drying for 8h at 90 ℃, and grinding to fine powder to obtain the carboxylated graphene sheet; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.%), and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of the catalyst in the step (1), 110g of polytetrahydrofuran ether glycol and 60g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 2h, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 6.25g of N-methyldiethanolamine and 45g of acetone into the prepolymer A, reacting for 3 hours at 85 ℃, adding 4g of 2,4, 6-trihydroxybenzoic acid, reacting for 3 hours at 75 ℃ at 1.8g of light-resistant agent in the step (2), adding 21.5g of triethylamine, neutralizing for 350 minutes, adding 90g of water, and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
3. The preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized by comprising the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.2g of sodium carboxymethylcellulose, 1.8g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst, wherein the yield is 70%;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3.5h in an ultrasonic cleaner with ultrasonic power of 400W and ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing by using deionized water until the deionized water is neutral, finally drying for 13h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of 99.5 (wt.)%, and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.3g of the catalyst in the step (1), 55g of polytetrahydrofuran ether glycol and 40g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 3h, adding 0.3g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500, and the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 2.8g of diisopropanolamine and 25.4g of acetone into the prepolymer A, reacting for 3 hours at 70 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.6g of the light-resistant agent in the step (2), reacting for 2 hours at 70 ℃, adding 14.2g of triethylamine to perform neutralization reaction for 40 minutes, adding 70g of water to perform emulsification, and obtaining the flame-retardant and light-resistant waterborne polyurethane coating.
4. The preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized by comprising the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst, wherein the yield is 70%;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2 graphene sheet into 300mL of concentrated sulfuric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluoro-benzene boric acid, mixing, reacting at 60 ℃, condensing and refluxing for 2h in an ultrasonic cleaner with ultrasonic power of 400W and ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length is 0.1-10 mu m, the width is 0.1-10 mu m, the thickness is 1-10 nm, the purity is 99.5 (wt.)%, and the specific surface area is 500-2600 m 2/g;
(4) mixing 2g of the catalyst in the step (1), 50g of polytetrahydrofuran ether glycol and 50g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 60 ℃ for 2h, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of the carboxylated graphene sheet in the step (3), reacting for 2h at the reaction temperature of 90 ℃, and obtaining a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding the prepolymer A; 2g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 18g of acetone, reacting for 2h at 65 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.4g of the light-resistant agent in the step (2), reacting at 75 ℃ for 0.5h, adding 12g of triethylamine to perform neutralization reaction for 30min, adding 110g of water, stirring and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
5. The preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized by comprising the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst, wherein the yield is 70%;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2 graphene sheet into 400mL concentrated nitric acid, 0.3g 4-triphenylamine borate and 0.2g 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 80 ℃, condensing and refluxing for 5h in an ultrasonic cleaner with the ultrasonic power of 400W and the ultrasonic frequency of 80KHz, diluting with 350mL deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, and grinding to fine powder, thus obtaining the carboxylated graphene sheet; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.%), and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of the catalyst in the step (1), 30g of polytetrahydrofuran ether glycol and 30g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting for 3h at 70 ℃, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of the carboxylated graphene sheet in the step (3), reacting for 2h, and reacting at the temperature of 90 ℃ to obtain a polyurethane prepolymer A;
(5) adding 5.25g of sulfanilic acid and 45g of acetone into the prepolymer A, reacting for 3.2h at 75 ℃, adding 3g of 2,4, 6-trihydroxybenzoic acid and 1.9g of the light-resistant agent in the step (2), reacting for 2h at 85 ℃, adding 22.5g of triethylamine to perform neutralization reaction for 360min, adding 100g of water to perform emulsification, and obtaining the flame-retardant and light-resistant waterborne polyurethane coating.
The invention has the following characteristics: according to the invention, polytetrahydrofuran ether glycol and isophorone diisocyanate react under the catalysis of dibutyltin dilaurate, dibutyltin dilaurate is fixed by using 2-sulfobenzoic anhydride, D-panthenol and 2,4, 6-trihydroxybenzoic acid react with residual isocyanate, and the flame retardance and the light resistance of polyurethane are improved. The concrete aspects are as follows:
(1) 3-hydroxy-7-methoxy-2-naphthoic acid, sodium carboxymethylcellulose, titanium trichloride, magnesium ethoxide, zinc acetate, diethanolamide and N-bromosuccinimide to prepare a novel catalyst, so that the toxicity of polyurethane is reduced, and the synthesis efficiency of polyurethane synthesis is improved;
(2) sodium sulfite, sodium metabisulfite, sodium tripolyphosphate, citric acid, tea polyphenol, dibutyl hydroxy toluene, aluminum carbonate and aluminum stearate, and methyl triethoxysilane and dimethylformamide to synthesize a light resisting agent;
(3) reacting carboxylated graphene with isocyanate, and grafting the reaction product into a polyurethane prepolymer;
(4) the 4-triphenylamine borate and the 3, 4, 5-trifluorobenzene boric acid can enhance the carboxylation degree of the graphene;
(5) aminobenzenesulfonic acid; n-methyldiethanolamine; diisopropanolamine; 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol; the chain extension effect is good when the aminobenzenesulfonic acid is subjected to chain extension.
Detailed Description
The invention is further illustrated by the following examples.
Example one
(1) Catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.05g of graphene sheet into 400mL of concentrated sulfuric acid, 0.4g of 4-triphenylamine borate and 0.3g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with the ultrasonic power of 500W and the ultrasonic frequency of 100KHz, diluting with 450mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 8h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.)%, and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of catalyst in the step (1), 80g of polytetrahydrofuran ether glycol and 40g of isophorone diisocyanate in a 500ml four-neck flask with a stirring paddle, a thermometer and a condensation tube, reacting for 1h at 70 ℃, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) 1.2g of aminobenzenesulfonic acid and 20g of acetone are added into the prepolymer A, the mixture is reacted for 2 hours at the temperature of 75 ℃, 1g of 2,4, 6-trihydroxybenzoic acid and 1.2g of the light-resistant agent in the step (2) are added, the reaction temperature is 85 ℃, the reaction time is 0.5 hour, 12g of triethylamine is added for neutralization reaction for 30 minutes, 110g of water is added, and the mixture is stirred and emulsified to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
Example two
(1) Catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.6g of sodium carboxymethylcellulose, 1.8g of titanium trichloride, 0.6g of magnesium ethoxide, 5.4g of zinc acetate, 4.6g of diethanolamine and 3.5g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.8g of sodium tripolyphosphate, 6.2g of citric acid, 4.8g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 2h, adding 4.2g of aluminum carbonate and 1.8g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.6g of dimethylformamide, and stirring at 80 ℃ for 2h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.4g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 90 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with the ultrasonic power of 500W and the ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with the deionized water until the deionized water is neutral, finally drying for 8h at 90 ℃, and grinding to fine powder to obtain the carboxylated graphene sheet; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.%), and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of the catalyst in the step (1), 110g of polytetrahydrofuran ether glycol and 60g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 2h, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 6.25g of N-methyldiethanolamine and 45g of acetone into the prepolymer A, reacting for 3 hours at 85 ℃, adding 4g of 2,4, 6-trihydroxybenzoic acid, reacting for 3 hours at 75 ℃ at 1.8g of light-resistant agent in the step (2), adding 21.5g of triethylamine, neutralizing for 350 minutes, adding 90g of water, and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
Example three
(1) Catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.2g of sodium carboxymethylcellulose, 1.8g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3.5h in an ultrasonic cleaner with ultrasonic power of 400W and ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing by using deionized water until the deionized water is neutral, finally drying for 13h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of 99.5 (wt.)%, and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.3g of the catalyst in the step (1), 55g of polytetrahydrofuran ether glycol and 40g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 3h, adding 0.3g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500, and the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 2.8g of diisopropanolamine and 25.4g of acetone into the prepolymer A, reacting for 3 hours at 70 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.6g of the light-resistant agent in the step (2), reacting for 2 hours at 70 ℃, adding 14.2g of triethylamine to perform neutralization reaction for 40 minutes, adding 70g of water to perform emulsification, and obtaining the flame-retardant and light-resistant waterborne polyurethane coating.
Example four
(1) Catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2 graphene sheet into 300mL of concentrated sulfuric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluoro-benzene boric acid, mixing, reacting at 60 ℃, condensing and refluxing for 2h in an ultrasonic cleaner with ultrasonic power of 400W and ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, and grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length is 0.1-10 mu m, the width is 0.1-10 mu m, the thickness is 1-10 nm, the purity is 99.5 (wt.)%, and the specific surface area is 500-2600 m 2/g;
(4) mixing 2g of the catalyst in the step (1), 50g of polytetrahydrofuran ether glycol and 50g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting at 60 ℃ for 2h, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of the carboxylated graphene sheet in the step (3), reacting for 2h at the reaction temperature of 90 ℃, and obtaining a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding the prepolymer A; 2g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 18g of acetone, reacting for 2h at 65 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.4g of the light-resistant agent in the step (2), reacting at 75 ℃ for 0.5h, adding 12g of triethylamine to perform neutralization reaction for 30min, adding 110g of water, stirring and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
Example five
(1) Catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to neutrality, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheet
Adding 0.2 graphene sheet into 400mL concentrated nitric acid, 0.3g 4-triphenylamine borate and 0.2g 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 80 ℃, condensing and refluxing for 5h in an ultrasonic cleaner with the ultrasonic power of 400W and the ultrasonic frequency of 80KHz, diluting with 350mL deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, and grinding to fine powder, thus obtaining the carboxylated graphene sheet; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 (wt.%), and the specific surface area of the graphene sheet is 500-2600 m 2/g;
(4) mixing 0.6g of the catalyst in the step (1), 30g of polytetrahydrofuran ether glycol and 30g of isophorone diisocyanate in a 500ml four-neck flask provided with a stirring paddle, a thermometer and a condensing tube, reacting for 3h at 70 ℃, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of the carboxylated graphene sheet in the step (3), reacting for 2h, and reacting at the temperature of 90 ℃ to obtain a polyurethane prepolymer A;
(5) adding 5.25g of sulfanilic acid and 45g of acetone into the prepolymer A, reacting for 3.2h at 75 ℃, adding 3g of 2,4, 6-trihydroxybenzoic acid and 1.9g of the light-resistant agent in the step (2), reacting for 2h at 85 ℃, adding 22.5g of triethylamine to perform neutralization reaction for 360min, adding 100g of water to perform emulsification, and obtaining the flame-retardant and light-resistant waterborne polyurethane coating.
The chemical raw materials (such as graphene) used by the invention can be purchased from any production or sales enterprises under the same name.
The beneficial effects of the present invention are further illustrated by the following relevant experimental data:
in order to quantitatively describe the light resistance of the coating, a spectrophotometer is adopted for detection to obtain a reversed color difference value △ E so as to describe the light resistance of the coating and the finish paint, △ E represents the color change degree, the larger △ E is, the more obvious the color change is, generally, the △ E value is slightly changed from 0 to 1.5, the △ E value is sensitively changed from 1.5 to 3.0, and the △ E value is obviously changed from 3.0 to 6.0 (see Wang Fang, Dang Gao, Wang Liqin, the photodegradation [ J ] of several organic cultural relic protection polymer coatings, the university of northwest reports 2005, 35 (5): 56-58), and the Mei paint PE paint is selected from Guangdong Mei Shi building materials Limited company.
TABLE shows the light resistance of the film formed by the graphene modified flame-retardant and light-resistant waterborne polyurethane coating
Figure DEST_PATH_IMAGE001
From Table one, it can be seen that the light fastness of the coatings prepared in examples one to five was within a slight range, showing good light fastness, whereas the market PU-1 was already of a sensible change at 390 min.
Flame retardancy is measured by the smoke density method (maximum smoke density, time to reach maximum smoke density), oxygen index, vertical burn index (flame burn time, flameless burn time).
Flame retardant property of film formed by epidiauxite modified flame retardant and light resistant waterborne polyurethane coating
Figure 758724DEST_PATH_IMAGE002
The detection of the indexes in the second table is based on the following standards respectively: the smoke density is determined according to GB8323-2008, and the oxygen index is determined by GB/T5454-1997 textile combustion performance test-oxygen index method; the flaming combustion time and flameless combustion time are determined by GB/T5455-1997 textile Combustion energy test-vertical method.
It can be seen from the table that after the graphene modified flame-retardant and light-resistant waterborne polyurethane coating disclosed by the invention is used, the maximum smoke density is obviously reduced, the time for reaching the maximum smoke density is obviously prolonged, the oxygen index is obviously improved, and the combustion time is obviously shortened.

Claims (5)

1. A furniture or metal appliance which is coated by the coating prepared by the preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized in that: the method comprises the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating to remove most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to be neutral, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light-resistant agent
Stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyl triethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.05g of graphene sheet into 400mL of concentrated sulfuric acid, 0.4g of 4-triphenylamine borate and 0.3g of 3, 4, 5-trifluoro-benzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with ultrasonic power of 500W and ultrasonic frequency of 100KHz, diluting with 450mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing the deionized water until the deionized water is neutral, finally drying for 8h at 80 ℃, grinding the deionized water into fine powder to obtain the carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 wt%, and the specific surface area of the graphene sheet2/g；
(4) In a 500mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 0.6g of the catalyst of step (1) was placed,
Mixing 80g of polytetrahydrofuran ether glycol with 40g of isophorone diisocyanate, reacting for 1h at 70 ℃, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃, and obtaining a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 1.2g of aminobenzenesulfonic acid and 20g of acetone into the prepolymer A, reacting for 2h at 75 ℃, adding 1g of 2,4, 6-trihydroxybenzoic acid and 1.2g of the light-resistant agent in the step (2), reacting at 85 ℃ for 0.5h, adding 12g of triethylamine to perform neutralization reaction for 30min, adding 110g of water, stirring, and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
2. A furniture or metal appliance which is coated by the coating prepared by the preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized in that: the preparation method comprises the following steps:
(1) catalyst synthesis
2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.6g of sodium carboxymethyl cellulose, 1.8g of titanium trichloride and ethanol
Adding 0.6g of magnesium, 5.4g of zinc acetate, 4.6g of diethanolamine and 3.5g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting at 90 ℃ for 3h, evaporating most of solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to be neutral, drying, mixing tetrahydrofuran, methanol and acetone, and recrystallizing to obtain a powder catalyst;
(2) synthesis of light-resistant agent
Stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.8g of sodium tripolyphosphate, 6.2g of citric acid, 4.8g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 2h, adding 4.2g of aluminum carbonate and 1.8g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyl triethoxysilane and 3.6g of dimethylformamide, and stirring at 80 ℃ for 2h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.4g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 90 ℃, condensing and refluxing for 3h in an ultrasonic cleaner with the ultrasonic power of 500W and the ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with the deionized water until the deionized water is neutral, finally drying for 8h at 90 ℃, and grinding to fine powder, thus obtaining the carboxylated graphene sheet; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 microns, the width of the graphene sheet is 0.1-10 microns, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 wt.%, and the specific surface area of the graphene sheet is 500-2600 m2/g；
(4) Mixing 0.6g of catalyst in the step (1), 110g of polytetrahydrofuran ether glycol and 60g of isophorone diisocyanate in a 500mL four-neck flask with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 2h, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) and (3) adding 6.25g of N-methyldiethanolamine and 45g of acetone into the prepolymer A, reacting for 3 hours at 85 ℃, adding 4g of 2,4, 6-trihydroxybenzoic acid and 1.8g of the light-resistant agent in the step (2), reacting at 75 ℃ for 3 hours, adding 21.5g of triethylamine, carrying out neutralization reaction for 350 minutes, adding 90g of water, and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
3. A furniture or metal appliance which is coated by the coating prepared by the preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized in that: the preparation method comprises the following steps:
(1) catalyst synthesis
2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.2g of sodium carboxymethyl cellulose, 1.8g of titanium trichloride and ethanol
Adding 0.6g of magnesium, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting at 90 ℃ for 3h, evaporating most of solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to be neutral, drying, mixing tetrahydrofuran, methanol and acetone, and recrystallizing to obtain a powder catalyst;
(2) synthesis of light-resistant agent
3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid and 4.5g of tea polyphenol
Stirring with 1.3g of dibutylhydroxytoluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyltriethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 300mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluorobenzene boric acid, mixing, reacting at 70 ℃, condensing and refluxing for 3.5h in an ultrasonic cleaner with the ultrasonic power of 400W and the ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration with a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with deionized water until the deionized water is neutral, finally drying for 13h at 80 ℃, grinding to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 mu m, the width of the graphene sheet is 0.1-10 mu m, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 wt%, and the specific surface area of the graphene sheet is 500-26002/g；
(4) In a 500mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 0.3g of the catalyst of step (1) was placed,
Mixing 55g of polytetrahydrofuran ether glycol with 40g of isophorone diisocyanate, reacting for 3h at 70 ℃, adding 0.3g of 2-sulfobenzoic anhydride and 0.05g of carboxylated graphene sheet in the step (3), reacting for 2h at 80 ℃, and obtaining a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding 2.8g of diisopropanolamine and 25.4g of acetone into the prepolymer A, reacting for 3 hours at 70 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.6g of the light-resistant agent in the step (2), reacting for 2 hours at 70 ℃, adding 14.2g of triethylamine to perform neutralization reaction for 40 minutes, adding 70g of water to perform emulsification, and obtaining the flame-retardant and light-resistant waterborne polyurethane coating.
4. A furniture or metal appliance which is coated by the coating prepared by the preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized in that: the preparation method comprises the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to be neutral, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light fastness agent:
stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyl triethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 300mL of concentrated sulfuric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluoro-benzene boric acid, mixing, reacting at 60 ℃, condensing and refluxing for 2h in an ultrasonic cleaner with ultrasonic power of 400W and ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration by using a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing the deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, and grinding the mixture to fine powder to obtain a carboxylated graphene sheet, wherein the graphene is a graphene sheet produced by a chemical vapor deposition method, and has the length of 0.1-10 mu m, the width of 0.1-10 mu m, the thickness of 1-10 nm, the purity of 99.5 wt.%, and the specific surface area of 500-2600 m 2/g;
(4) mixing 2g of the catalyst in the step (1), 50g of polytetrahydrofuran ether glycol and 50g of isophorone diisocyanate in a 500mL four-neck flask with a stirring paddle, a thermometer and a condensing tube, reacting at 60 ℃ for 2h, adding 0.2g of 2-sulfobenzoic anhydride and 0.05g of the carboxylated graphene sheet in the step (3), reacting for 2h at 90 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 500;
(5) adding the prepolymer A; 2g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 18g of acetone, reacting for 2h at 65 ℃, adding 1.6g of 2,4, 6-trihydroxybenzoic acid and 1.4g of the light-resistant agent in the step (2), reacting at 75 ℃ for 0.5h, adding 12g of triethylamine to perform neutralization reaction for 30min, adding 110g of water, stirring and emulsifying to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
5. A furniture or metal appliance which is coated by the coating prepared by the preparation method of the graphene modified flame-retardant and light-resistant waterborne polyurethane coating is characterized in that: the preparation method comprises the following steps:
(1) catalyst synthesis
Adding 2.2g of 3-hydroxy-7-methoxy-2-naphthoic acid, 4.1g of sodium carboxymethylcellulose, 1.6g of titanium trichloride, 0.6g of magnesium ethoxide, 5.3g of zinc acetate, 4.5g of diethanolamine and 3.2g of N-bromosuccinimide into 30mL of methyl ethyl ketone and 2mL of p-toluenesulfonyl chloride, reacting for 3h at 90 ℃, evaporating most of the solvent, cooling and filtering, washing a filter cake with hot potassium bicarbonate solution, washing with water to be neutral, drying, mixing tetrahydrofuran, methanol and acetone for recrystallization to obtain a powder catalyst;
(2) synthesis of light-resistant agent
Stirring 3g of sodium sulfite, 0.9g of sodium metabisulfite, 3.5g of sodium tripolyphosphate, 6.2g of citric acid, 4.5g of tea polyphenol and 1.3g of dibutyl hydroxy toluene at 60 ℃ for 1h, adding 4.2g of aluminum carbonate and 1.6g of aluminum stearate, stirring at 70 ℃ for 2h, adding 2.5g of methyl triethoxysilane and 3.2g of dimethylformamide, and stirring at 80 ℃ for 3h to obtain a light-resistant agent;
(3) carboxylated graphene sheets
Adding 0.2g of graphene sheet into 400mL of concentrated nitric acid, 0.3g of 4-triphenylamine borate and 0.2g of 3, 4, 5-trifluoro-phenylboronic acid, mixing, reacting at 80 ℃, condensing and refluxing for 5h in an ultrasonic cleaner with the ultrasonic power of 400W and the ultrasonic frequency of 80KHz, diluting with 350mL of deionized water after ultrasonic treatment, then performing suction filtration with a microporous filter membrane with the diameter of 0.2 mu m, repeatedly washing with the deionized water until the deionized water is neutral, finally drying for 12h at 80 ℃, grinding, and drying for 12hObtaining a carboxylated graphene sheet after being in a fine powder state; the graphene is a graphene sheet produced by a chemical vapor deposition method, the length of the graphene sheet is 0.1-10 microns, the width of the graphene sheet is 0.1-10 microns, the thickness of the graphene sheet is 1-10 nm, the purity of the graphene sheet is 99.5 wt.%, and the specific surface area of the graphene sheet is 500-2600 m2/g；
(4) Mixing 0.6g of catalyst, 30g of polytetrahydrofuran ether glycol and 30g of isophorone diisocyanate in the step (1) in a 500mL four-neck flask with a stirring paddle, a thermometer and a condensing tube, reacting at 70 ℃ for 3h, adding 0.6g of 2-sulfobenzoic anhydride and 0.75g of carboxylated graphene sheet in the step (3), reacting for 2h, and reacting at the temperature of 90 ℃ to obtain a polyurethane prepolymer A;
(5) and (2) adding 5.25g of sulfanilic acid and 45g of acetone into the prepolymer A, reacting for 3.2h at 75 ℃, adding 3g of 2,4, 6-trihydroxybenzoic acid and 1.9g of the light-resistant agent in the step (2), reacting for 2h at 85 ℃, adding 22.5g of triethylamine, performing neutralization reaction for 360min, and adding 100g of water for emulsification to obtain the flame-retardant and light-resistant waterborne polyurethane coating.
CN201810881113.5A 2016-08-31 2016-08-31 Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances Active CN108949002B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810881113.5A CN108949002B (en) 2016-08-31 2016-08-31 Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810881113.5A CN108949002B (en) 2016-08-31 2016-08-31 Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances
CN201610775497.3A CN106366896B (en) 2016-08-31 2016-08-31 The preparation method of graphene modified flame-retardant, light-resistant waterborne polyurethane coating

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201610775497.3A Division CN106366896B (en) 2016-08-31 2016-08-31 The preparation method of graphene modified flame-retardant, light-resistant waterborne polyurethane coating

Publications (2)

Publication Number Publication Date
CN108949002A CN108949002A (en) 2018-12-07
CN108949002B true CN108949002B (en) 2020-06-19

Family

ID=57901884

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201810881113.5A Active CN108949002B (en) 2016-08-31 2016-08-31 Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances
CN201610775497.3A Active CN106366896B (en) 2016-08-31 2016-08-31 The preparation method of graphene modified flame-retardant, light-resistant waterborne polyurethane coating

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201610775497.3A Active CN106366896B (en) 2016-08-31 2016-08-31 The preparation method of graphene modified flame-retardant, light-resistant waterborne polyurethane coating

Country Status (1)

Country Link
CN (2) CN108949002B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942785B (en) * 2019-02-26 2021-03-12 昆山嘉力普制版胶粘剂油墨有限公司 Preparation method of carboxylated graphene oxide modified carboxylic acid type waterborne polyurethane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194607A (en) * 2014-08-15 2014-12-10 段小宁 Preparation method of light-resistant and waterproof water-based flame retardant polyurethane coating and adhesive
CN104804169A (en) * 2015-05-22 2015-07-29 烟台大学 Preparation method of graphene-modified polyurethane conductive coating
CN105153921A (en) * 2015-10-26 2015-12-16 烟台大学 Method for preparing aqueous polyurethane coating and adhesive modified through carbon nanotubes and graphene

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140151596A1 (en) * 2012-11-30 2014-06-05 Energyguard Atlantic, Llc Thermally conductive, corrosion resistant coatings
KR101573309B1 (en) * 2014-01-16 2015-12-01 주식회사 노루홀딩스 Polyurethane composition for cavitation resistance and method of forming film using the same
CN103897495B (en) * 2014-04-21 2015-10-14 烟台大学 A kind of preparation method of fire-retardant and lightfast coating material
CN104087144B (en) * 2014-07-21 2016-03-02 段小宁 The preparation method of a kind of waterproof and Antibacterial polyurethane coating
CN104087145B (en) * 2014-07-21 2016-03-02 段宝荣 A kind of fire-retardant preparation method with germ resistance aqueous polyurethane coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194607A (en) * 2014-08-15 2014-12-10 段小宁 Preparation method of light-resistant and waterproof water-based flame retardant polyurethane coating and adhesive
CN104804169A (en) * 2015-05-22 2015-07-29 烟台大学 Preparation method of graphene-modified polyurethane conductive coating
CN105153921A (en) * 2015-10-26 2015-12-16 烟台大学 Method for preparing aqueous polyurethane coating and adhesive modified through carbon nanotubes and graphene

Also Published As

Publication number Publication date
CN108949002A (en) 2018-12-07
CN106366896B (en) 2018-10-09
CN106366896A (en) 2017-02-01

Similar Documents

Publication Publication Date Title
US9909030B2 (en) Method for preparing carbon nanotubes graphene modified aqueous polyurethane coatings and adhesives
CN106519239B (en) A kind of preparation method and its usage of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant
CN102666726A (en) Resin crosslinking agent
CN102471632A (en) Aqueous polymer dispersion as a binding agent for plasters and coating materials having improved fire behavior
KR102365803B1 (en) Fluorine-containing polymers
CN103540243A (en) Nano flame-retardant coating
CN112794987B (en) Flame-retardant polyurea-polyurethane
CN108949002B (en) Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances
CN108531065A (en) A kind of preparation method of the aqueous polyurethane coating of high-temp resistant fire-retarding
CN101302232A (en) Perfluoro alkyl phosphoester acrylic ester and preparation thereof
CN101280053B (en) Method for preparing acrylic-modified waterborneppolyurethane from reproducible polylol
CN104087149A (en) Method for preparing light-fast waterborne polyurethane coating material
US9701863B2 (en) Self-renewing hydrophilic organic coatings
CN107955515B (en) Flame-retardant, light-resistant and low-VOC polyurethane coating
CN109797398A (en) A kind of application of Diaryl iodonium salt compound as metal inhibitor
US11512165B2 (en) Polymers, processes, compositions and uses
CN104073149A (en) Preparation method for lightproof and waterproof polyurethane coating
CN110272343A (en) A kind of starlike molecular structure Hinered phenols antioxidant and its synthesis and application
Macocinschi et al. Aromatic polysulfones for flame retardancy
CN103897495B (en) A kind of preparation method of fire-retardant and lightfast coating material
CN109651589A (en) A kind of preparation method containing N, P extinguishing waterborn polyurethane
CN115894835A (en) Biomass-based phosphorus-based copolymerized flame-retardant waterborne polyurethane and preparation method and application thereof
CN107298769B (en) A kind of phenyl modified expansible graphite fire retardant and preparation method thereof
CN104004449A (en) Method for preparing light-resistant and flame-resistant aqueous polyurethane coatings
CN107164973A (en) A kind of preparation method of environmental-protection flame-retardant uvioresistant TPU synthetic leather

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
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20200519

Address after: 323000 No.1, Yangshan industrial community, Xinjian Town, Jinyun County, Lishui City, Zhejiang Province

Applicant after: Zhejiang Jiajia smart home Co., Ltd

Address before: 264003 No. 16-2 Fuqing Street, Zhifu District, Yantai City, Shandong Province

Applicant before: Duan Baorong

GR01 Patent grant
GR01 Patent grant