CN107955515B - Flame-retardant, light-resistant and low-VOC polyurethane coating - Google Patents
Flame-retardant, light-resistant and low-VOC polyurethane coating Download PDFInfo
- Publication number
- CN107955515B CN107955515B CN201711369135.5A CN201711369135A CN107955515B CN 107955515 B CN107955515 B CN 107955515B CN 201711369135 A CN201711369135 A CN 201711369135A CN 107955515 B CN107955515 B CN 107955515B
- Authority
- CN
- China
- Prior art keywords
- reacting
- stirring
- manganese hypophosphite
- flame
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant, light-resistant and low-VOC polyurethane coating and a preparation method thereof.0.22 g of triethylene tetramine, 70g of polytetrahydrofuran ether glycol and 15g of hexamethylene diisocyanate are added into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and the mixture is reacted for 2 hours at 80 ℃ to obtain a polyurethane prepolymer A; adding 0.62g of acetamide and 8.2g of methyl ethyl ketone into the prepolymer A, reacting for 3.5h at 75 ℃, adding 2g of modified manganese hypophosphite prepared in the step (1), 4g of 4-carboxyphenylboronic acid and 2.5g of diethylenetriamine pentamethylenephosphonic acid, reacting for 2h at 80 ℃, adding 7.1g of triethylamine for neutralization reaction for 60min, adding 0.9g of vitamin C and 70g of water, stirring and emulsifying to obtain the polyurethane coating with flame retardance, light fastness and low VOC.
Description
The application is a divisional application of patent application with application number 201610761160.7 entitled polyurethane coating preparation method with flame resistance, light resistance and low VOC.
Technical Field
The invention relates to a preparation method of a polyurethane coating, in particular to a preparation method of a polyurethane coating with flame retardance, light resistance and low VOC.
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, how to fix the residual tin catalyzed by dibutyltin dilaurate and reduce the harm degree of polyurethane coating residues to the environment 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.
The water-based polyurethane (also called water-based polyurethane) is a polyurethane resin containing hydrophilic groups in the molecular chain of polyurethane, has strong affinity with water, and can be dispersed in water by adopting a specific process to form a stable system. The waterborne polyurethane is mainly applied to the aspects of leather finishing, textile printing and dyeing, paper industry, building coatings, adhesives, cast steel coatings and the like, and almost all the related materials are flammable materials, and the materials are inevitably potential safety hazards of fire if the materials are not subjected to flame retardant treatment when in use. The flame retardance of the waterborne polyurethane is one of the important directions for the functionalization of the waterborne polyurethane.
Polyurethane coatings, i.e., urethane coatings, have a substantial number of polyurethane linkages in the coating film molecule. The polyurethane coating contains not only the urethane bond, but also the urea bond, the ether bond, the ester bond and the allophanate bond, and is a coating with excellent performance and wide application
VOC (volatile Organic Compounds) refers to volatile solvents in solvent-based coatings that can cause illness upon contact or inhalation by humans. Polyurethane coatings often contain VOCs. VOC has great harm to the health of human bodies, not only has an erosion effect on the skin, but also has stimulation and destruction effects on the central nervous system, hematopoietic organs and respiratory system of the human bodies, can cause symptoms such as headache, nausea, chest distress, hypodynamia, vomiting and the like, and can be twitch, coma and even die in severe cases. The economic losses from environmental damage and human injury caused by the use of toxic chemical solvent-based coatings worldwide are as high as billions of dollars each year. Thus, the world
The main coating producing countries in the world have developed regulations for limiting VOC emission. For example, internationally, according to the European Community ecological sign product-the regulation of VOC related limit, the most used coating for home decoration of people is 30 g/L, and the national mandatory standard of national coating of China, namely the VOC is regulated to be not more than 200 g/L in the limit of harmful substances in interior wall coating of interior decoration and decoration materials. Therefore, the development of low VOC polyurethane coatings is the direction of polyurethane coating development.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a polyurethane coating with flame retardance, light resistance and low VOC, effectively fixing by selecting a catalyst to reduce the toxicity, improve the polymerization yield and reduce the VOC content.
The technical scheme of the invention is as follows:
1. the preparation method of the polyurethane coating with flame retardance, light resistance and low VOC is characterized by comprising the following steps:
(1) and preparing modified manganese hypophosphite: adding 9g of manganese hypophosphite, 23g of boric acid, 20g of diethanolamine, 6.2g of hexaphenoxycyclotriphosphazene, 2.6g of 3-aminopropyltrihydroxysilane and 60g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.22g of triethylene tetramine, 70g of polytetrahydrofuran ether glycol and 15g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting for 2 hours at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.62g of acetamide and 8.2g of methyl ethyl ketone into the prepolymer A, reacting for 3.5h at 75 ℃, adding 2g of modified manganese hypophosphite prepared in the step (1), 4g of 4-carboxyphenylboronic acid and 2.5g of diethylenetriamine pentamethylene phosphonic acid, reacting for 2h at 80 ℃, adding 7.1g of triethylamine for neutralization reaction for 60min, adding 0.9g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
2. The preparation method of the polyurethane coating with flame retardance, light resistance and low VOC is characterized by comprising the following steps:
(1) and preparing modified manganese hypophosphite: adding 6g of manganese hypophosphite, 10g of boric acid, 15g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4-hydroxy phenethylamine and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of ethylene diamine tetraacetic acid dipotassium, and stirring for reaction for 1h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.64g of carbodiimide, 65g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting at 90 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.2g of dithiothreitol and 16.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 6g of modified manganese hypophosphite prepared in the step (1), 3.4g of 4-carboxyphenylboronic acid and 2.2g of amino trimethylene phosphonic acid, reacting for 2h at 95 ℃, adding 13.5g of triethylamine for neutralization reaction for 50min, adding 2.7g of 4, 8-dihydroxyquinoline-2-formic acid and 100g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
3. The preparation method of the polyurethane coating with flame retardance, light resistance and low VOC is characterized by comprising the following steps:
(1) and preparing modified manganese hypophosphite: adding 4.2g of manganese hypophosphite, 26g of boric acid, 22g of diethanolamine, 12g of hexamethylol melamine, 2.2g of 4, 8-dihydroxy quinoline-2-formic acid and 45g of water into a 250ml three-neck flask with a stirrer and a thermometer, adjusting the pH value to 4, heating to 70 ℃, stirring for reaction for 1h, stirring for reaction for 2g of ethylene diamine tetraacetic acid at 50 ℃ for 1h to obtain modified manganese hypophosphite;
(2) adding 0.32g of sebacic dihydrazide, 85g of polytetrahydrofuran ether glycol and 32g of hexamethylene diisocyanate into a 500ml three-necked flask with a stirrer, a condenser tube and a thermometer, and reacting for 1h at 75 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 2.4g of hexahydro-sym-triazoborane and 20.4g of methyl ethyl ketone into the prepolymer A, reacting for 2.0h at 70 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 3.8g of 4-carboxyphenylboronic acid and 2.6g of triallyl cyanurate, reacting at 75 ℃ for 2.5h, adding 15.2g of triethylamine, neutralizing for 30min, adding 2.2g of sodium salicylate and 150g of water, stirring, and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
4. The preparation method of the polyurethane coating with flame retardance, light resistance and low VOC is characterized by comprising the following steps:
(1) and preparing modified manganese hypophosphite: adding 6.2g of manganese hypophosphite, 13g of boric acid, 22g of diethanolamine, 8.5g of hexaphenoxycyclotriphosphazene, 3.5g of 3-aminopropyltrihydroxysilane and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 3 hours, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2 hours at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.15g of acetyl tributyl citrate, 60g of polytetrahydrofuran ether glycol and 20g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting at 80 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.52g of acetamide and 9.2g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 60 ℃, adding 4g of modified manganese hypophosphite prepared in the step (1), 3.6g of 4-carboxyphenylboronic acid and 2.5g of trimethylolpropane trimethacrylate, reacting for 2h at 70 ℃, adding 7.5g of triethylamine for neutralization reaction for 40min, adding 1.6g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
5. The preparation method of the polyurethane coating with flame retardance, light resistance and low VOC is characterized by comprising the following steps:
(1) and preparing modified manganese hypophosphite: adding 3g of manganese hypophosphite, 10g of boric acid, 35g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4, 8-dihydroxy quinoline-2-formic acid and 70g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 2h, adding 2g of ethylene diamine tetraacetic acid, and stirring for reaction for 2h at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.84g of 5-aminotetrazole, 80g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked bottle with a stirrer, a condenser tube and a thermometer, and reacting at 90 ℃ for 2 hours to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.9g of dithiothreitol and 24.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 6.4g of 4-carboxyphenylboronic acid and 3.8g of cyanuric acid, reacting at 85 ℃ for 2h, adding 14.5g of triethylamine, neutralizing for 60min, stirring and emulsifying 3.7g of 4, 8-dihydroxyquinoline-2-formic acid and 75g of water, and obtaining the flame-retardant, light-resistant and low-VOC polyurethane coating.
The invention has the advantages that:
(1) triethylene tetramine, carbodiimide, sebacic dihydrazide, acetyl tributyl citrate and 5-aminotetrazole have the advantages of replacing traditional tin compound catalysts;
(2) the HDI polyurethane has the advantages that the polymer is crosslinked by diethylenetriamine penta-methylene phosphonic acid, amino trimethylene phosphonic acid, triallyl cyanurate, trimethylolpropane trimethacrylate and cyanuric acid, so that the defect of low strength of the traditional HDI polyurethane is overcome, and meanwhile, the reactant is chelated, so that the absorption of small molecules is increased, and the released VOC is reduced;
(3) acetamide, dithiothreitol and hexahydro-sym-triazborane not only have chain extenders, but also have light resistance;
(4) the hexaphenoxycyclotriphosphazene, the melamine cyanurate and the hexamethylol melamine have a flame retardant effect, and the 3-aminopropyl trihydroxysilane, the 4-hydroxyphenylethylamine and the 4, 8-dihydroxyquinoline-2-formic acid have a synergistic effect on flame retardance and improve the flame retardance of the flame retardant.
Detailed Description
The invention is further illustrated by the following examples.
Example one
(1) And preparing modified manganese hypophosphite: adding 9g of manganese hypophosphite, 23g of boric acid, 20g of diethanolamine, 6.2g of hexaphenoxycyclotriphosphazene, 2.6g of 3-aminopropyltrihydroxysilane and 60g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.22g of triethylene tetramine, 70g of polytetrahydrofuran ether glycol and 15g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting for 2 hours at 80 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.62g of acetamide and 8.2g of methyl ethyl ketone into the prepolymer A, reacting for 3.5h at 75 ℃, adding 2g of modified manganese hypophosphite prepared in the step (1), 4g of 4-carboxyphenylboronic acid and 2.5g of diethylenetriamine pentamethylene phosphonic acid, reacting for 2h at 80 ℃, adding 7.1g of triethylamine for neutralization reaction for 60min, adding 0.9g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
Example two
(1) And preparing modified manganese hypophosphite: adding 6g of manganese hypophosphite, 10g of boric acid, 15g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4-hydroxy phenethylamine and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of ethylene diamine tetraacetic acid dipotassium, and stirring for reaction for 1h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.64g of carbodiimide, 65g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting at 90 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.2g of dithiothreitol and 16.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 6g of modified manganese hypophosphite prepared in the step (1), 3.4g of 4-carboxyphenylboronic acid and 2.2g of amino trimethylene phosphonic acid, reacting for 2h at 95 ℃, adding 13.5g of triethylamine for neutralization reaction for 50min, adding 2.7g of 4, 8-dihydroxyquinoline-2-formic acid and 100g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
Example three
(1) And preparing modified manganese hypophosphite: adding 4.2g of manganese hypophosphite, 26g of boric acid, 22g of diethanolamine, 12g of hexamethylol melamine, 2.2g of 4, 8-dihydroxy quinoline-2-formic acid and 45g of water into a 250ml three-neck flask with a stirrer and a thermometer, adjusting the pH value to 4, heating to 70 ℃, stirring for reaction for 1h, stirring for reaction for 2g of ethylene diamine tetraacetic acid at 50 ℃ for 1h to obtain modified manganese hypophosphite;
(2) adding 0.32g of sebacic dihydrazide, 85g of polytetrahydrofuran ether glycol and 32g of hexamethylene diisocyanate into a 500ml three-necked flask with a stirrer, a condenser tube and a thermometer, and reacting for 1h at 75 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 2.4g of hexahydro-sym-triazoborane and 20.4g of methyl ethyl ketone into the prepolymer A, reacting for 2.0h at 70 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 3.8g of 4-carboxyphenylboronic acid and 2.6g of triallyl cyanurate, reacting at 75 ℃ for 2.5h, adding 15.2g of triethylamine, neutralizing for 30min, adding 2.2g of sodium salicylate and 150g of water, stirring, and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
Example four
(1) And preparing modified manganese hypophosphite: adding 6.2g of manganese hypophosphite, 13g of boric acid, 22g of diethanolamine, 8.5g of hexaphenoxycyclotriphosphazene, 3.5g of 3-aminopropyltrihydroxysilane and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 3 hours, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2 hours at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.15g of acetyl tributyl citrate, 60g of polytetrahydrofuran ether glycol and 20g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting at 80 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.52g of acetamide and 9.2g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 60 ℃, adding 4g of modified manganese hypophosphite prepared in the step (1), 3.6g of 4-carboxyphenylboronic acid and 2.5g of trimethylolpropane trimethacrylate, reacting for 2h at 70 ℃, adding 7.5g of triethylamine for neutralization reaction for 40min, adding 1.6g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
Example five
(1) And preparing modified manganese hypophosphite: adding 3g of manganese hypophosphite, 10g of boric acid, 35g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4, 8-dihydroxy quinoline-2-formic acid and 70g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 2h, adding 2g of ethylene diamine tetraacetic acid, and stirring for reaction for 2h at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.84g of 5-aminotetrazole, 80g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked bottle with a stirrer, a condenser tube and a thermometer, and reacting at 90 ℃ for 2 hours to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.9g of dithiothreitol and 24.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 6.4g of 4-carboxyphenylboronic acid and 3.8g of cyanuric acid, reacting at 85 ℃ for 2h, adding 14.5g of triethylamine, neutralizing for 60min, stirring and emulsifying 3.7g of 4, 8-dihydroxyquinoline-2-formic acid and 75g of water, and obtaining the flame-retardant, light-resistant and low-VOC polyurethane coating.
The beneficial effects of the present invention are further illustrated by the following relevant experimental data: PU-1 is a polyurethane corrosion resistant topcoat selected from the group consisting of the tin-free commercial billows chemical Co.
Table one film-forming property of polyurethane coating with flame retardance, light resistance and low VOC
| Experimental group | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | PU-1 |
| Hardness of | B | B | B | B | B | B |
| Adhesion/grade | 3 | 2 | 3 | 3 | 2 | 2 |
| Flexibility/mm | 3 | 3 | 3 | 2 | 3 | 2 |
From the second table, it can be seen that the film has better properties in terms of appearance, hardness, adhesion, and flexibility.
Mechanical properties of films from flame retardant, light resistant and low VOC polyurethane coatings
| Experimental group | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | PU-1 |
| Elongation at break/% | 162 | 158 | 161 | 167 | 172 | 157 |
| Tensile strength/MPa | 5.9 | 5.6 | 5.2 | 7.4 | 8.8 | 5.4 |
| Wear/grade resistance | 3.0 | 4 | 4.0 | 3.5 | 4.5 | 3 |
The detection method of the indexes in the second table is referred to (Jiangqi. physicochemical inspection of leather finished product [ M ]. China light industry Press, 1999), and the film obtained by the coating has better performances of elongation at break, tensile strength and abrasion resistance.
The flame retardance is measured by a smoke density method (maximum smoke density and time for reaching the maximum smoke density), an oxygen index and a vertical combustion index (flaming combustion time and flameless combustion time), and the elongation at break represents the mechanical property of the flame-retardant flame-.
Flame retardancy of film obtained from polyurethane coating with flame retardancy, light resistance and low VOC
| Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | PU-1 | |
| Maximum smoke density | 12 | 26 | 32 | 16 | 11 | 59 |
| Time to maximum smoke density/s | 180 | 180 | 195 | 225 | 185 | 150 |
| Oxygen index | 27.6 | 26.8 | 24.9 | 26.8 | 27.2 | 24.1 |
| Flame combustion time/s | 12.5 | 15.8 | 10.6 | 9.9 | 7.2 | 24 |
| Flameless combustion time/s | 0.1 | 0.2 | 0 | 0 | 0 | 1 |
The detection of the indexes in the table three is respectively based on the following standards: 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.
As can be seen from the third table, when the film prepared by the invention, the light-resistant polyurethane coating and the adhesive is combusted, 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.
In order to quantitatively describe the light resistance of the paint, a spectrophotometer is adopted for detection to obtain a reversed color difference value △ E to describe the light resistance of the paint and the finish paint, △ E represents the color change degree, and 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 paints, the journal of northwest, 2005, 35 (5): 56-58).
TABLE IV flame retardance, light resistance and light resistance of films obtained from Low VOC polyurethane coatings
| Time/min | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | PU-1 |
| 90 | 0.1 | 0.2 | 0.3 | 0.2 | 0.1 | 0.2 |
| 150 | 0.3 | 0.3 | 0.4 | 0.5 | 0.2 | 0.3 |
| 270 | 0.5 | 0.4 | 0.4 | 0.5 | 0.4 | 0.6 |
| 330 | 0.7 | 0.8 | 0.5 | 0.5 | 0.4 | 0.9 |
| 390 | 0.8 | 0.8 | 0.7 | 0.7 | 0.5 | 1.0 |
| 450 | 0.9 | 0.8 | 0.7 | 0.7 | 0.6 | 1.2 |
| 510 | 1.0 | 1.1 | 0.9 | 0.9 | 0.6 | 1.9 |
| 540 | 1.1 | 1.2 | 1.1 | 0.9 | 0.8 | 2.2 |
| 600 | 1.3 | 1.2 | 1.2 | 1.2 | 0.8 | 2.8 |
From Table four, 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 PU-1 was already within a sensible range at 510 min.
The test is carried out according to the limit standard of harmful substances in GB24408-2009 exterior wall coating:
TABLE V flame-retardant, light-resistant and low VOC polyurethane coating VOC
| Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | PU-1 | |
| Volatile Organic Compound (VOC) content | 106 | 112 | 134 | 146 | 137 | 215 |
Claims (5)
1. The flame-retardant, light-resistant and low-VOC polyurethane coating is prepared by the following steps:
(1) and preparing modified manganese hypophosphite: adding 9g of manganese hypophosphite, 23g of boric acid, 20g of diethanolamine, 6.2g of hexaphenoxycyclotriphosphazene, 2.6g of 3-aminopropyltrihydroxysilane and 60g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.22g of triethylene tetramine, 70g of polytetrahydrofuran ether glycol and 15g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser pipe and a thermometer, and reacting at 80 ℃ for 2 hours to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.62g of acetamide and 8.2g of methyl ethyl ketone into the prepolymer A, reacting for 3.5h at 75 ℃, adding 2g of modified manganese hypophosphite prepared in the step (1), 4g of 4-carboxyphenylboronic acid and 2.5g of diethylenetriamine pentamethylene phosphonic acid, reacting for 2h at 80 ℃, adding 7.1g of triethylamine for neutralization reaction for 60min, adding 0.9g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
2. The flame-retardant, light-resistant and low-VOC polyurethane coating is prepared by the following steps: (1) and preparing modified manganese hypophosphite: adding 6g of manganese hypophosphite, 10g of boric acid, 15g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4-hydroxy phenethylamine and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 1h, adding 2g of ethylene diamine tetraacetic acid dipotassium, and stirring for reaction for 1h at 60 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.64g of carbodiimide, 65g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked bottle with a stirrer, a condenser tube and a thermometer, and reacting at 90 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.2g of dithiothreitol and 16.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 6g of modified manganese hypophosphite prepared in the step (1), 3.4g of 4-carboxyphenylboronic acid and 2.2g of amino trimethylene phosphonic acid, reacting for 2h at 95 ℃, adding 13.5g of triethylamine for neutralization reaction for 50min, adding 2.7g of 4, 8-dihydroxyquinoline-2-formic acid and 100g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
3. The flame-retardant, light-resistant and low-VOC polyurethane coating is prepared by the following steps: (1) and preparing modified manganese hypophosphite: adding 4.2g of manganese hypophosphite, 26g of boric acid, 22g of diethanolamine, 12g of hexamethylol melamine, 2.2g of 4, 8-dihydroxy quinoline-2-formic acid and 45g of water into a 250ml three-neck flask with a stirrer and a thermometer, adjusting the pH value to 4, heating to 70 ℃, stirring for reaction for 1h, stirring for reaction for 2g of ethylene diamine tetraacetic acid at 50 ℃ for 1h, and obtaining modified manganese hypophosphite;
(2) adding 0.32g of sebacic dihydrazide, 85g of polytetrahydrofuran ether glycol and 32g of hexamethylene diisocyanate into a 500ml three-necked flask with a stirrer, a condenser tube and a thermometer, and reacting for 1h at 75 ℃ to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 2.4g of hexahydro-sym-triazoborane and 20.4g of methyl ethyl ketone into the prepolymer A, reacting for 2.0h at 70 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 3.8g of 4-carboxyphenylboronic acid and 2.6g of triallyl cyanurate, reacting at 75 ℃ for 2.5h, adding 15.2g of triethylamine, neutralizing for 30min, adding 2.2g of sodium salicylate and 150g of water, stirring, and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
4. The flame-retardant, light-resistant and low-VOC polyurethane coating is prepared by the following steps: (1) and preparing modified manganese hypophosphite: adding 6.2g of manganese hypophosphite, 13g of boric acid, 22g of diethanolamine, 8.5g of hexaphenoxycyclotriphosphazene, 3.5g of 3-aminopropyltrihydroxysilane and 40g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 3 hours, adding 2g of dipotassium ethylenediamine tetraacetate, and stirring for reaction for 2 hours at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.15g of acetyl tributyl citrate, 60g of polytetrahydrofuran ether glycol and 20g of hexamethylene diisocyanate into a 250ml three-necked bottle with a stirrer, a condenser and a thermometer, and reacting at 80 ℃ for 2h to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000;
(3) adding 0.52g of acetamide and 9.2g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 60 ℃, adding 4g of modified manganese hypophosphite prepared in the step (1), 3.6g of 4-carboxyphenylboronic acid and 2.5g of trimethylolpropane trimethacrylate, reacting for 2h at 70 ℃, adding 7.5g of triethylamine for neutralization reaction for 40min, adding 1.6g of vitamin C and 70g of water, stirring and emulsifying to obtain the flame-retardant, light-resistant and low-VOC polyurethane coating.
5. The flame-retardant, light-resistant and low-VOC polyurethane coating is prepared by the following steps:
(1) and preparing modified manganese hypophosphite: adding 3g of manganese hypophosphite, 10g of boric acid, 35g of diethanolamine, 12g of melamine cyanurate, 2.8g of 4, 8-dihydroxy quinoline-2-formic acid and 70g of water into a 250ml three-necked bottle with a stirrer and a thermometer, adjusting the pH to 4, heating to 70 ℃, stirring for reaction for 2h, adding 2g of ethylene diamine tetraacetic acid, and stirring for reaction for 2h at 50 ℃ to obtain modified manganese hypophosphite;
(2) adding 0.84g of 5-aminotetrazole, 80g of polytetrahydrofuran ether glycol and 40g of hexamethylene diisocyanate into a 500ml three-necked flask with a stirrer, a condenser tube and a thermometer, and reacting at 90 ℃ for 2 hours to obtain a polyurethane prepolymer A, wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000;
(3) adding 3.9g of dithiothreitol and 24.5g of methyl ethyl ketone into the prepolymer A, reacting for 2.5h at 75 ℃, adding 8.9g of modified manganese hypophosphite prepared in the step (1), 6.4g of 4-carboxyphenylboronic acid and 3.8g of cyanuric acid, reacting at 85 ℃ for 2h, adding 14.5g of triethylamine, neutralizing for 60min, stirring and emulsifying 3.7g of 4, 8-dihydroxyquinoline-2-formic acid and 75g of water, and obtaining the flame-retardant, light-resistant and low-VOC polyurethane coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711369135.5A CN107955515B (en) | 2016-08-30 | 2016-08-30 | Flame-retardant, light-resistant and low-VOC polyurethane coating |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610761160.7A CN106221550B (en) | 2016-08-30 | 2016-08-30 | Fire-retardant, light resistance and low VOC polyurethane coating preparation method |
| CN201711369135.5A CN107955515B (en) | 2016-08-30 | 2016-08-30 | Flame-retardant, light-resistant and low-VOC polyurethane coating |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610761160.7A Division CN106221550B (en) | 2016-08-30 | 2016-08-30 | Fire-retardant, light resistance and low VOC polyurethane coating preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107955515A CN107955515A (en) | 2018-04-24 |
| CN107955515B true CN107955515B (en) | 2020-05-08 |
Family
ID=58071761
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610761160.7A Active CN106221550B (en) | 2016-08-30 | 2016-08-30 | Fire-retardant, light resistance and low VOC polyurethane coating preparation method |
| CN201711369135.5A Active CN107955515B (en) | 2016-08-30 | 2016-08-30 | Flame-retardant, light-resistant and low-VOC polyurethane coating |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610761160.7A Active CN106221550B (en) | 2016-08-30 | 2016-08-30 | Fire-retardant, light resistance and low VOC polyurethane coating preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN106221550B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575227A (en) * | 2018-12-27 | 2019-04-05 | 王世茸 | The fire-retardant PU resin of environment-friendly type antibiotic |
| CN109706747A (en) * | 2018-12-27 | 2019-05-03 | 王世茸 | Flame-retardant leather brick and its embroidering method |
| CN111285989B (en) * | 2020-02-07 | 2021-11-05 | 山东理工大学 | Preparation of high-performance reaction type polyurethane flame retardant compounded by cyclic triphosphazenyl hexaphosphoric acid and derivative thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861852A (en) * | 2015-06-22 | 2015-08-26 | 朱明德 | Method for preparing flame-retardant water-based polyurethane coating and adhesive for building |
| CN105176368A (en) * | 2015-10-26 | 2015-12-23 | 烟台大学 | Preparation method of polyurethane coating and adhesive with flame retardance and light resistance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140151596A1 (en) * | 2012-11-30 | 2014-06-05 | Energyguard Atlantic, Llc | Thermally conductive, corrosion resistant coatings |
| CN103073696B (en) * | 2013-01-30 | 2014-08-13 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
| CN104109457B (en) * | 2014-08-12 | 2016-03-23 | 段小宁 | A kind of fire-retardant with water-repellancy aqueous polyurethane coating and the preparation method of tackiness agent |
-
2016
- 2016-08-30 CN CN201610761160.7A patent/CN106221550B/en active Active
- 2016-08-30 CN CN201711369135.5A patent/CN107955515B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861852A (en) * | 2015-06-22 | 2015-08-26 | 朱明德 | Method for preparing flame-retardant water-based polyurethane coating and adhesive for building |
| CN105176368A (en) * | 2015-10-26 | 2015-12-23 | 烟台大学 | Preparation method of polyurethane coating and adhesive with flame retardance and light resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106221550B (en) | 2018-02-16 |
| CN106221550A (en) | 2016-12-14 |
| CN107955515A (en) | 2018-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107955515B (en) | Flame-retardant, light-resistant and low-VOC polyurethane coating | |
| CN100567357C (en) | A kind of preparation method of fluorinated water based polyurethane | |
| CN104203900B (en) | The compound of (methyl) acroleic acid esterification of radiation-hardenable | |
| CN100588664C (en) | Water acrylic resin and preparing method thereof | |
| CN105176368B (en) | A kind of preparation method of fire-retardant and sunproof polyurethane coating and adhesive | |
| CN105153921A (en) | Method for preparing aqueous polyurethane coating and adhesive modified through carbon nanotubes and graphene | |
| CN104356915B (en) | A kind of fire-retardant preparation method with water proofing property aqueous polyurethane coating | |
| Ma et al. | A facile strategy to construct vegetable oil-based, fire-retardant, transparent and mussel adhesive intumescent coating for wood substrates | |
| CN104087149B (en) | A kind of preparation method of light-resistant waterborne polyurethane coating | |
| EP2383254A1 (en) | Radiation curable amino(meth)acrylates | |
| CN108219101A (en) | Excellent dual cure urethane acrylate of a kind of chemical resistance and preparation method thereof | |
| CN104745070B (en) | A kind of polyurethane exterior wall antiseptic fire-retardation coating and preparation method thereof | |
| CN104109457B (en) | A kind of fire-retardant with water-repellancy aqueous polyurethane coating and the preparation method of tackiness agent | |
| CN104530365B (en) | A kind of leather surface processing aqueous polyurethane and preparation method thereof | |
| CN115403994A (en) | Aspartame polyurea solvent-free matte odor-free coating and preparation method thereof | |
| CN104073149A (en) | Preparation method for lightproof and waterproof polyurethane coating | |
| CN104004449B (en) | A kind of fast light preparation method with aqueous flame retardant polyurethane coating | |
| CN106221551B (en) | Fire-retardant, waterproof and low VOC polyurethane coating preparation method | |
| CN115260852B (en) | EB flame-retardant spraying varnish and preparation method thereof | |
| BR112013012629A2 (en) | ethylenically unsaturated hydroxyl terminated polyuterane, radiation curable composition, coating composition, paint or varnish, and, article | |
| KR20090038269A (en) | Aqueous polyurethane clear coating material useful as a finishing coating of automobiles possessing antibacterial properties | |
| CN103087621A (en) | Antibacterial waterborne polyurethane wood lacquer | |
| CN107056840A (en) | A kind of preparation method of response type nitrogen phosphorus fire retardant | |
| CN108949002B (en) | Preparation method of flame-retardant and light-resistant waterborne polyurethane coating for preparing furniture or metal appliances | |
| CN104861846A (en) | Waterborne polyurethane based quick-drying wood coating with superhigh solid content |
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 |
Effective date of registration: 20200410 Address after: 213000 Xin'an village, Hengshan Town, Wujin District, Jiangsu, Changzhou Applicant after: Changzhou Huaxing anticorrosive material Co., Ltd Address before: 264005 School of chemical engineering, Yantai University, 30 Qingquan Road, Laishan District, Shandong, Yantai Applicant before: Duan Baorong |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |