CN113861813A - Cured polyester resin coating and preparation method thereof - Google Patents
Cured polyester resin coating and preparation method thereof Download PDFInfo
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- CN113861813A CN113861813A CN202111274145.7A CN202111274145A CN113861813A CN 113861813 A CN113861813 A CN 113861813A CN 202111274145 A CN202111274145 A CN 202111274145A CN 113861813 A CN113861813 A CN 113861813A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a normal temperature curing polyester resin coating and a preparation method thereof, and the coating has the performances of high-speed curing, corrosion resistance, fluidity, flexibility, chemical stability, weather resistance, chlorine resistance, thermal stability, ultraviolet irradiation resistance and the like. The paint mainly comprises polyester resin, epoxy resin, organic silicon resin, organic phosphorus resin and the like. The polyester resin adopted by the invention adopts neopentyl glycol, terephthalic acid, end-capping agent isophthalic acid, polyhydric alcohol, polybasic acid and other raw materials, the synthesized polyester resin is matched with epoxy resin for production, and the ethyl triphenyl phosphonium bromide curing accelerator is added to replace the traditional quaternary ammonium salt accelerator, so that the chemical reaction speed is accelerated; the polyester resin improves the feeding process, adopts a new process of neopentyl glycol and terephthalic acid alternate feeding method in the production process, has simple preparation method and lower cost, and has good market application prospect.
Description
Technical Field
The invention relates to a polyester resin coating, in particular to a normal-temperature curing polyester resin coating and a preparation method thereof.
Background
The powder coating has the characteristics of energy conservation, no VOC emission, good decoration, safe use and the like, and the domestic powder coating technology is rapidly developed in recent years. Have been used in many applications for various metal substrates, including architectural coatings on aluminum, and coatings on steel in agriculture, the building industry, and in the application industry. These applications require excellent coating adhesion, corrosion resistance to the protective substrate, pigment wetting and weatherability. In other powder coating applications, such as coatings comprising bound metal flake pigments, which coatings comprise corrodible materials, excellent corrosion resistance is required, as well as excellent pigment wetting and coating adhesion. The mixed powder coating is also called polyester-epoxy mixed powder coating, the existing mixed polyester resin can achieve excellent single performance, but the performance indexes are usually considered when being adjusted, and the compatibility cannot be achieved.
Therefore, there is an urgent need to develop a coating material having excellent overall properties such as high-rate curing, corrosion resistance, fluidity, flexibility, chemical stability, weather resistance, chlorine resistance, thermal stability and ultraviolet irradiation resistance.
Disclosure of Invention
One of the objects of the present invention is to provide a room temperature curing polyester resin coating, which can be cured at a high rate and has excellent corrosion resistance, fluidity, flexibility, chemical stability, weather resistance, chlorine resistance, thermal stability and ultraviolet irradiation resistance.
The second purpose of the invention is to provide a preparation method of the normal temperature curing polyester resin coating.
The first purpose of the invention is realized by the following technical scheme: a normal temperature curing polyester resin coating comprises the following components in parts by weight:
the above components are further preferably:
the above components are further preferably:
the polyester resin is formed by polybasic acid and polyhydric alcohol, the acid value of the polyester resin is 30-60 mgKOH/g, the glass transition temperature Tg is as follows: 80-105 ℃, softening point: 130-160 ℃ and the viscosity is 90-120mpa.s/175 ℃. Further preferred is an acid value: 30-60 mgKOH/g, softening point: 150-160 ℃ and glass transition temperature Tg: polyester resin at 95-105 ℃ and at 50-60mpa.s/175 ℃.
The preparation method specifically comprises the steps of adding 30-60% of polybasic acid, 10-50% of polyhydric alcohol and 0.01-1% of catalyst into a reaction kettle with a stirrer, a thermometer, a fractionating column and a nitrogen inlet, mixing, introducing nitrogen, heating to 100-300 ℃, carrying out esterification reaction, and carrying out vacuum polycondensation at 150-250 ℃ until the reaction liquid is completely clarified to reach an acid value of 30-60 mgKOH/g and a viscosity of 90-120mpa.s/175 ℃. The molecular weight of the polyester resin is controlled to be 5000-.
The polybasic acid can be terephthalic acid, isophthalic acid, phthalic acid and naphthalene dicarboxylic acid; or the polybasic acid can be trifunctional or multifunctional acid such as trimellitic anhydride, pyromellitic acid, 1, 3, 5-trimellitic acid, etc. Preferably, terephthalic acid is the reactant and isophthalic acid is the endcapping agent.
The polyhydric alcohol can be neopentyl glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol. Neopentyl glycol is preferred.
The catalyst may be monobutyl dihydroxy tin chloride, tetrabutyl titanate or isopropyl titanate.
In the preparation process, the neopentyl glycol and the terephthalic acid are alternately added, so that the viscosity can be better controlled.
The preparation process of the epoxy resin comprises the following steps:
(1) putting bisphenol A into a dissolving kettle according to a proportion, adding epoxy chloropropane and a tertiary amine catalyst, stirring and heating to 100 ℃ for dissolving;
(2) feeding the dissolved materials to a reaction kettle, dividing a 30% NaOH solution into two equal parts, completely dropwise adding a first part of the 30% NaOH solution into the materials in the reaction kettle within 3-5 hours at the temperature of 60-75 ℃ while stirring, continuously reacting for 3-5 hours at the temperature of 60-75 ℃, and recovering excessive epoxy chloropropane under reduced pressure after the reaction is finished;
(3) adding a toluene solution into the materials in the reaction kettle after recovery, stirring and heating to 60-75 ℃, completely dropwise adding a second 30% NaOH solution into the materials in the reaction kettle at the temperature within 45 minutes, continuously reacting at 60-75 ℃ for 2-4 hours, cooling, standing and layering, separating an upper layer of resin toluene solution, moving to a reflux dehydration kettle, adding toluene into salt feet at a lower layer, extracting once again, separating an upper layer of resin benzene solution, combining the two resin toluene solutions, and moving to the reflux dehydration kettle;
(4) and refluxing the resin toluene solution in a reflux dehydration kettle until the distilled benzene is clear and anhydrous, cooling, standing, filtering, then sending to a benzene removing kettle for removing toluene, removing benzene at normal pressure until the liquid temperature reaches over 130 ℃, and then removing toluene under reduced pressure to obtain the epoxy resin. Epoxy equivalent of the epoxy resin: 700-850 g/ep, melt viscosity: 700-985 cps @150 ℃, softening point (G, max.): 70-90 ℃.
The organic silicon resin comprises the following raw materials in parts by mole:
the catalyst is chloroplatinic acid.
The preparation method comprises the following steps:
(1): slowly dripping trimethoxy silane into methyl acrylate and a chloroplatinic acid catalyst, mixing and reacting at the reaction temperature of 60-100 ℃, then preserving heat for 1-3 hours, and removing low-boiling-point substances under reduced pressure;
(2): adding tetraethoxysilane into the reactant obtained in the step (1), and quickly stirring for 2-4 hours at the reaction temperature of 50-100 ℃;
(3): after the reaction is finished, adding toluene and sodium carbonate to adjust the pH value of the solution to be between 6 and 7, standing for layering, washing the upper layer to be neutral, and removing low-boiling-point substances through decompression to obtain the finished product of the organic silicon resin.
The solvent is one or two of toluene, xylene and cyclohexane.
The molecular weight of the organic silicon resin is 3000-8000 dalton, and the viscosity is 30-50mpa.s/175 ℃.
The organophosphorus polyesters of the present invention are prepared by adding a phosphorus-containing acid, suitably a phosphorus-containing acid such as phosphoric acid, phosphorous acid, phosphinic acid, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, organic acid phosphates, phosphorus oxychloride, alkyl esters of phosphoric acid, anhydrides of phosphoric acid, hydrogen-containing phosphates, hydrogen-containing hypophosphites, hydrogen-containing phosphites, hydrogen-containing orthophosphates, hydrogen-containing polyphosphates, hydrogen-containing metaphosphates, and mixtures thereof, to the polyester resin during the preparation process. Preferably, the phosphorus-containing acid is selected from the group consisting of orthophosphoric acid, polyphosphoric acid, metaphosphoric acid, salts thereof, mixtures thereof, and mixtures thereof with other phosphorus-containing acids.
Organophosphorus resins can be prepared in large quantities by condensing one or more polyols with an excess (on an equivalent basis) of an acid comprising one or more phosphorus-containing acids or their hydrochloric acids. Suitable amounts of the phosphorus-containing acid as reactant may range from 0.1 to 10 wt%, preferably from 0.5 to 3 wt%, more preferably up to 1.5 wt%. To ensure the proper molecular weight, in one embodiment, the organophosphorus resin can be formed in two steps, including mixing a phosphorus-containing acid, a polyacid, and an excess of a polyol to react them to form a hydroxyl functional polyester resin containing a phosphate ester linkage; the hydroxyl functional polyester is then end-capped with one or more polyacids to produce a phosphorus-containing polyester. Or by reacting an excess of a polyol with a polyacid to form a hydroxyl functional polyester. A phosphorus-containing acid is then added, and the reaction temperature is optionally raised, to form a hydroxyl-functional polyester resin containing a phosphate ester linkage. Finally, the formed polyester is end-capped with a polyacid to prepare the organophosphorus resin.
The curing agent is ethyl triphenyl phosphonium bromide.
The auxiliary agent of the invention can be conventional auxiliary agent, for example, one or a mixture of more of leveling agent, benzoin, air permeability agent, brightener, electrical agent and accelerator.
The filler is one or a mixture of more of titanium dioxide, barium sulfate, silica micropowder, calcium carbonate, mica powder and superfine aluminum powder.
The pigment of the invention adopts weather-resistant inorganic pigments, such as: one or more of iron oxide red, carbon black and iron oxide yellow.
The preparation method of the coating comprises the following steps: weighing polyester resin, epoxy resin, organic silicon resin, organic phosphorus resin, curing agent, auxiliary agent, filler and pigment according to a proportion, placing the materials in a mixing tank, fully mixing and crushing the materials to obtain a mixed premixed material; feeding the mixed premixed material into a double-screw extruder for extrusion; and tabletting the extruded material by a tabletting machine, cooling, crushing, screening and packaging.
The main technical innovation points of the new product are as follows:
(1) the invention adopts polyester resin, epoxy resin, organic silicon resin and organic phosphorus resin as the main components of the coating, and adjusts the proper proportion of the components, thereby leading the coating of the coating to be cured at high speed and having excellent corrosion resistance, fluidity, flexibility, chemical stability, weather resistance, chlorine resistance, thermal stability and ultraviolet irradiation resistance.
(2) The polyester resin adopted by the invention adopts neopentyl glycol, terephthalic acid, end-capping agent isophthalic acid, polyhydric alcohol, polybasic acid and other raw materials, the synthesized polyester resin is matched with epoxy resin for production, and the ethyl triphenyl phosphonium bromide curing accelerator is added to replace the traditional quaternary ammonium salt accelerator, so that the chemical reaction speed is accelerated;
(3) the polyester resin adopted by the invention improves the feeding process, and a new process of neopentyl glycol and terephthalic acid alternate feeding method is adopted in the production process, so that the viscosity in the production process is controlled at 90-120mpa.s/175 ℃, and the polyol and the polyacid are introduced, thereby improving the performance of the polyester resin and endowing the resin with hardness and chemical resistance;
(4) the organic silicon resin is convenient to prepare and proper in viscosity, can be used in combination with polyester resin and epoxy resin organic phosphorus resin, can improve the adhesion and adhesive force of the coating, and is better combined with a sprayed object especially on a metal surface;
(5) the organic phosphorus resin can increase the corrosion resistance of the coating, adjust the dosage of the organic phosphorus resin, ensure the corrosion resistance of the coating, ensure the excellent coating adhesion and weather resistance of the coating, avoid the addition of harmful anticorrosive agents and ensure that the coating is green and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to examples
Example 1: preparation of polyester resin
(1) Adding 26Kg of neopentyl glycol and 10Kg of water into a reaction kettle, and heating to melt;
(2) adding 52kg of terephthalic acid and 0.1kg of monobutyl dihydroxy tin chloride in sequence, introducing nitrogen and continuously heating to 160 ℃;
(3) after reacting for a period of time, adding 26Kg of neopentyl glycol and 10Kg of water, heating and stirring;
(4) adding 52kg of terephthalic acid and 0.1kg of monobutyl dihydroxy tin chloride in sequence, introducing nitrogen and continuously heating to 160 ℃;
(5) heating the mixture from 160 ℃ to 270 ℃ until the acid value reaches 18mgKOH/g, carrying out polycondensation reaction by first vacuumizing, adding 0.24kg of acid hydrolysis agent isophthalic acid when the acid value reaches 6mgKOH/g, the softening point is 100 ℃ and the melt viscosity at 200 ℃ is 90-120mpa.s, carrying out acid hydrolysis reaction, carrying out acidolysis reaction by second vacuumizing when the acid value reaches 70mgKOH/g, and stopping reaction when the acid value of the reaction product is about 45mgKOH/g and the hydroxyl value is less than 15mgKOH/g to obtain the polyester resin. The acid value of the polyester resin is 30-50 mgKOH/g, and the molecular weight of the polyester resin is 8000-12000 daltons.
Example 2: preparation of epoxy resins
(1) Putting 12Kg of bisphenol A into a dissolving kettle, adding 3.8Kg of epoxy chloropropane and 0.6Kg of tetrabutyl tertiary amine catalyst, stirring and heating to 100 ℃ for dissolving;
(2) feeding the dissolved materials to a reaction kettle, dividing a 30% NaOH solution into two equal parts, completely dropwise adding a first part of the 30% NaOH solution into the materials in the reaction kettle within 3-5 hours at the temperature of 60-75 ℃ while stirring, continuously reacting for 3-5 hours at the temperature of 60-75 ℃, and recovering excessive epoxy chloropropane under reduced pressure after the reaction is finished;
(3) adding a toluene solution into the materials in the reaction kettle after recovery, stirring and heating to 60-75 ℃, completely dropwise adding a second 30% NaOH solution into the materials in the reaction kettle at the temperature within 45 minutes, continuously reacting at 60-75 ℃ for 2-4 hours, cooling, standing and layering, separating an upper layer of resin toluene solution, moving to a reflux dehydration kettle, adding toluene into salt feet at a lower layer, extracting once again, separating an upper layer of resin benzene solution, combining the two resin toluene solutions, and moving to the reflux dehydration kettle;
(4) and refluxing the resin toluene solution in a reflux dehydration kettle until the distilled benzene is clear and anhydrous, cooling, standing, filtering, then sending to a benzene removing kettle for removing toluene, removing benzene at normal pressure until the liquid temperature reaches over 130 ℃, and then removing toluene under reduced pressure to obtain the epoxy resin. Epoxy equivalent of the epoxy resin: 700-850 g/ep, melt viscosity: 700-985 cps @150 ℃, softening point (G, max.): 70-90 ℃.
Example 3: preparation of silicone resins
(1): adding 10Kg of methyl acrylate, 0.3Kg of chloroplatinic acid catalyst and a toluene solvent into a reaction kettle, slowly dropwise adding 5Kg of trimethoxy silane, mixing and reacting at the reaction temperature of 100 ℃, then preserving heat for 1 hour, and removing low-boiling-point substances by decompression;
(2): adding 20Kg of tetraethoxysilane into the reactant obtained in the step (1), and quickly stirring for 2 hours at the reaction temperature of 100 ℃;
(3): after the reaction is finished, adding toluene and sodium carbonate to adjust the pH value of the solution to be between 6 and 7, standing for layering, washing the upper layer to be neutral, and removing low-boiling-point substances through decompression to obtain the finished product of the organic silicon resin. The molecular weight of the organic silicon resin is 5000-.
Example 4: preparation of organophosphorus resins
(1) Adding 26Kg of neopentyl glycol and 10Kg of water into a reaction kettle, and heating to melt;
(2) adding 45Kg of terephthalic acid, 1.2Kg of phosphoric acid and 0.1Kg of monobutyl dihydroxy tin chloride in sequence, introducing nitrogen, and continuously heating to 160 ℃;
(3) heating the mixture from 160 ℃ to 270 ℃ until the acid value reaches 18mgKOH/g, carrying out polycondensation reaction by first vacuumizing, adding 0.18kg of acid hydrolysis agent isophthalic acid when the acid value reaches 6mgKOH/g, the softening point is 100 ℃ and the melt viscosity at 200 ℃ is 90-120mpa.s, carrying out acid hydrolysis reaction, carrying out acidolysis reaction by second vacuumizing when the acid value reaches 70mgKOH/g, and stopping reaction when the acid value of the reaction product is about 45mgKOH/g and the hydroxyl value is less than 15mgKOH/g to obtain the polyester resin. The acid value of the polyester resin is 30-50 mgKOH/g, and the molecular weight of the polyester resin is 8000-12000 daltons.
Example 5: preparation of the coating
(a) Weighing the components with the acid values according to a proportion, wherein the curing agent is ethyl triphenyl phosphonium bromide, the auxiliary agent is 1 part of titanium dioxide and 2 parts of barium sulfate, and the filler is placed in a mixing tank, fully mixed and crushed for 1-10 minutes;
(b) feeding the crushed material into a double-screw extruder for extrusion; controlling the heating temperature of the extruder to be 80-120 ℃;
(c) and tabletting, cooling and crushing the extruded material into powder with the particle size (equivalent particle size D50) of 30-45 um by using a crusher, and then sieving and packaging to obtain the material.
Example 6: preparation of the coating
The preparation was carried out as in example 5.
Example 7: preparation of the coating
The above components are further preferably:
the preparation was carried out as in example 5.
Example 8: preparation of the coating
The above components are further preferably:
the preparation was carried out as in example 5.
Example 9: preparation of the coating
The preparation was carried out as in example 5.
Example 10: and (5) testing the performance of the coating.
The following evaluations were made of the properties of the powder and of the powder coating obtained from the powder:
film thickness: using POSITECTORTMDry film thickness was determined on a 600-FN1 type coating thickness gauge, where the film thickness on a ferrous substrate was measured according to ASTM D1186-01 Test method B-electronic Meter "non-destructive Standard measurement of Dry film thickness of non-magnetic coating applied on a ferrous substrate (Standard Test)Methods for the determination of the non-destructive measuring of Dry Film Thickness of non-magnetic Coatings Applied to a Ferrous Base the Film Thickness on non-Ferrous substrates was determined according to ASTM D1400-00 "non-destructive Standard Measurement of Dry Film Thickness of non-magnetic Coatings Applied on non-Ferrous Metal substrates (Standard Test Methods for non-destructive measuring of Dry Film Thickness of non-magnetic Coatings Applied to a non-Ferrous Metal Base)". Film thickness is the range of three readings (low to high) measured at the central portion of the sample plate.
204 ℃ gel time: 1/8 teaspoons of the coating powder to be tested were dropped onto the flat plate electric furnace and a timer was started. The sample was stirred using the end of a wood stir bar with sufficient speed of motion that samples in the 1 inch diameter range were mixed and melted. Stirring was continued and periodically the stir bar was lifted to a position about 2 inches high from the flat plate furnace. When the paddle was raised, the material was considered to have gelled if it no longer formed a continuous strand between the flat plate electric furnace and the paddle. The gel time shows how fast the powder formulation can be cured at a particular temperature. An acceptable gel time needs to be shorter than the cure time in the application at the test temperature.
20 ° gloss and 60 ° gloss: the Gloss of the cured coatings was measured according to ASTM D523-89, "Standard Test Method for Specular Gloss", using a ByK-Gardner micro-TRI-Gloss instrument (Byk-Gardner USA, 9104Guilford Road, Columbia, MD21406 USA). The gloss reading is the average of three readings near the center of the sample and the results are recorded at 20 ° and 60 °. The 60 ° gloss reading has the following meanings: 0-10: a very low gloss-textured finish or a smooth matte finish; 10-30: low gloss; 30-70: medium gloss; 70+ high gloss. 20 gloss is used to compare samples having 60 gloss values greater than 70.
PCI smoothness: coating smoothness was determined by observing and comparing the orange peel (surface roughness) of the exemplary coatings to a set of coating smoothness standards, which were graded from 1-10, with 1 representing the roughest surface and 10 being the smoothest surface. The Coating smoothness standards are provided by Powder Coating Institute (PCI), Alexandria, VA.
Salt spray aluminum: coatings applied to bare Q A aluminum panels of 76.2 mm X152.4 mm X0.60 mm (3 inches X6 inches X0.25 inches) from Q-Lab, Cleveland, USA were subjected to a Salt Spray corrosion test using a sharp metal edge to cut an X-shaped scratch (approximately 75 mm in circumference and 40 mm in width) in the coating through the coating to the metal substrate according to ASTM B117-03 "Standard Practice for Operating Salt Spray Apparatus" (2003). The coated panels were considered to fail in the salt spray corrosion test when the coating was 0.80 mm free (peeled) of the substrate from the initial scratch. The longer the time elapsed before the sample failed in the salt spray test, the better the corrosion resistance/protection of the coating/substrate system.
Salt spray steel B-1000: the coatings applied to 76.2 mm by 152.4 mm by 0.66 mm (3 inch by 6 inch by 0.26 inch) polished B1000P60DIWACT cold rolled steel panels of ACT Laboratories, inc. were subjected to a Salt Spray corrosion test using a Standard Practice for Operating Salt Spray Apparatus (Fog) according to ASTM B117-03 "Standard Practice" test for Standard Spray coating ", which steel panels were treated with iron phosphate, sealed with chromium, rinsed with deionized water, and tested using a sharp metal blade to cut X-shaped scratches (about 75 mm on a perimeter and about 40 mm wide) through the coating to the metal substrate. The coated panels were considered to fail in the salt spray corrosion test when the coating was 0.80 mm free (peeled) of the substrate from the initial scratch. The longer the time elapsed before the sample failed in the salt spray test, the better the corrosion resistance/protection of the coating/substrate system.
Table 1: powder coating test results
From the above test data, it can be seen that the coatings of the present invention have excellent corrosion resistance, high rate of set and corrosion resistance, flow, flexibility, chemical stability, weatherability, chlorine resistance, thermal stability and resistance to ultraviolet radiation.
Claims (10)
1. A normal temperature curing polyester resin coating is characterized in that: the coating comprises the following components in parts by weight:
2. the ambient temperature curing polyester resin coating of claim 1, wherein the polyester resin is prepared by the following method: adding 30-60% of polybasic acid, 10-50% of polyalcohol and 0.01-1% of catalyst into a reaction kettle with a stirrer, a thermometer, a fractionating column and a nitrogen inlet, mixing, introducing nitrogen, heating to 100-300 ℃, carrying out esterification reaction, and after the reaction liquid is completely clarified, carrying out vacuum polycondensation at the temperature of 150-250 ℃ until the acid value is 30-60 mgKOH/g, the viscosity is 90-120mpa.s/175 ℃, and the molecular weight of the polyester resin is 5000-;
the polybasic acid is terephthalic acid, isophthalic acid, phthalic acid and naphthalene dicarboxylic acid; or the polybasic acid is trimellitic anhydride, pyromellitic acid and 1, 3, 5-trimellitic acid;
the polyhydric alcohol is neopentyl glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol or triethylene glycol;
the catalyst is monobutyl dihydroxy tin chloride, tetrabutyl titanate or isopropyl titanate.
3. The normal temperature curing polyester resin coating as claimed in claim 1, wherein the epoxy resin is prepared by the following method:
(1) putting bisphenol A into a dissolving kettle, adding epoxy chloropropane and a tertiary amine catalyst, stirring and heating to 100 ℃ for dissolving;
(2) feeding the dissolved materials to a reaction kettle, dividing a 30% NaOH solution into two equal parts, completely dropwise adding a first part of the 30% NaOH solution into the materials in the reaction kettle within 3-5 hours at the temperature of 60-75 ℃ while stirring, continuously reacting for 3-5 hours at the temperature of 60-75 ℃, and recovering excessive epoxy chloropropane under reduced pressure after the reaction is finished;
(3) adding a toluene solution into the materials in the reaction kettle after recovery, stirring and heating to 60-75 ℃, completely dropwise adding a second 30% NaOH solution into the materials in the reaction kettle at the temperature within 45 minutes, continuously reacting at 60-75 ℃ for 2-4 hours, cooling, standing and layering, separating an upper layer of resin toluene solution, moving to a reflux dehydration kettle, adding toluene into salt feet at a lower layer, extracting once again, separating an upper layer of resin benzene solution, combining the two resin toluene solutions, and moving to the reflux dehydration kettle;
(4) and refluxing the resin toluene solution in a reflux dehydration kettle until the distilled benzene is clear and anhydrous, cooling, standing, filtering, then sending to a benzene removing kettle for removing toluene, removing benzene at normal pressure until the liquid temperature reaches over 130 ℃, and then removing toluene under reduced pressure to obtain the epoxy resin.
4. The normal temperature curing polyester resin coating as claimed in claim 1, wherein the raw materials of the silicone resin comprise the following components in parts by mole:
the catalyst is chloroplatinic acid;
the preparation method of the organic silicon resin comprises the following steps:
(1): slowly dripping trimethoxy silane into methyl acrylate and a chloroplatinic acid catalyst, mixing and reacting at the reaction temperature of 60-100 ℃, then preserving heat for 1-3 hours, and removing low-boiling-point substances under reduced pressure;
(2): adding tetraethoxysilane into the reactant obtained in the step (1), and quickly stirring for 2-4 hours at the reaction temperature of 50-100 ℃;
(3): after the reaction is finished, adding toluene and sodium carbonate to adjust the pH value of the solution to be between 6 and 7, standing for layering, washing the upper layer to be neutral, and removing low-boiling-point substances through decompression to obtain the finished product of the organic silicon resin.
5. An ambient curing polyester resin coating as claimed in claim 1, wherein said organic phosphorus polyester is prepared by adding phosphorus-containing acid during the preparation of polyester resin, and suitable phosphorus-containing acid is phosphoric acid, phosphorous acid, phosphinic acid, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, organic acid phosphate, phosphorus oxychloride, alkyl ester of phosphoric acid, anhydride of phosphoric acid, hydrogen-containing phosphate, hydrogen-containing hypophosphite, hydrogen-containing phosphite, hydrogen-containing orthophosphate, hydrogen-containing polyphosphate, hydrogen-containing metaphosphate, and their mixture.
6. The normal temperature curing polyester resin coating as claimed in claim 1, wherein the curing agent is ethyl triphenyl phosphonium bromide.
7. The normal temperature curing polyester resin coating as claimed in claim 1, wherein the auxiliary agent is one or more of benzoin, air-permeable agent, brightener, electrical agent and accelerator.
8. The normal temperature curing polyester resin coating as claimed in claim 1, wherein the filler is one or a mixture of more of titanium dioxide, barium sulfate, silica powder, calcium carbonate, mica powder and ultrafine aluminum powder.
9. The ambient temperature curing polyester resin coating as claimed in claim 1, wherein the pigment is one or more selected from iron oxide red, carbon black and iron oxide yellow.
10. The method for preparing a polyester resin coating capable of being cured at normal temperature according to claim 1, wherein the polyester resin, the epoxy resin, the organic silicon resin, the organic phosphorus resin, the curing agent, the auxiliary agent, the filler and the pigment are weighed in proportion, placed in a mixing cylinder, fully mixed and crushed to obtain a mixed premixed material; feeding the mixed premixed material into a double-screw extruder for extrusion; and tabletting the extruded material by a tabletting machine, cooling, crushing, screening and packaging.
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