CN113150658B - Corrosion-resistant weather-resistant flame-retardant polyester resin for powder coating - Google Patents
Corrosion-resistant weather-resistant flame-retardant polyester resin for powder coating Download PDFInfo
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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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
- C09D5/033—Powdery paints characterised by the additives
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention relates to the technical field of powder coatings, in particular to a polyester resin, a powder coating and a coating for a corrosion-resistant weather-resistant flame-retardant powder coating, which comprise the following components in parts by weight: 102-138 parts of terephthalic acid, 26-38 parts of fluorine-containing dicarboxylic acid, 79-108 parts of isophthalic acid, 56-78 parts of neopentyl glycol, 20-28 parts of propylene glycol and 22-30 parts of fluorine-containing dihydric alcohol; through reasonable collocation of the components, the polyester resin not only has improved flame retardant property, but also keeps better glass transition temperature, and has excellent corrosion resistance and weather resistance.
Description
Technical Field
The invention relates to the technical field of powder coatings, in particular to a polyester resin for a corrosion-resistant weather-resistant flame-retardant powder coating, a powder coating and a coating.
Background
At present, most of steel-plastic pipelines are still subjected to corrosion prevention by adopting a traditional paint coating process, so that the environment pollution is caused, the production efficiency is low, the waste of raw materials is serious, the corrosion prevention effect is poor, the adhesion force is poor, the paint surface is easy to peel off, the coating needs to be carried out again at intervals, no harmful substance is generated in the production process and the actual use of the powder coating, the powder coating belongs to an environment-friendly corrosion prevention material, the adsorption force with the pipelines is strong, the service life is long, the production process is simple, the corrosion prevention efficiency is greatly improved, the powder coating is widely applied to the pipeline industry, and for example, the corrosion prevention engineering of the steel-plastic pipelines is mostly coated by the powder coating.
For example, chinese patent CN101058694a discloses a fire-retardant powder coating for ultra-thin steel structure, which is characterized in that: the tetrabromobisphenol A epoxy resin comprises the following components in percentage by mass: 66.0 to 66.5 percent of tetrabromobisphenol A, 13.0 to 13.6 percent of epichlorohydrin, 5.8 to 6.0 percent of sodium hydroxide and 14.0 to 15.0 percent of water, and the formula of the powder fireproof powder coating comprises the following components in percentage by mass: tetrabromobisphenol A epoxy resin 45-60%, dicyandiamide 2.2-3%, ammonium polyphosphate 15-21%, melamine 10-14%, dipentaerythritol 5-7%, flatting agent 0.5-2%, benzoin 0.3-0.5%, and titanium dioxide 5-10%.
Chinese patent CN1380370A discloses a non-expansive epoxy polyester mixed type fireproof powder coating which is characterized in that the coating is prepared by heating, mixing, extruding, crushing and sieving epoxy resin, polyester resin, auxiliary agents, fillers, pigments and flame retardants, and the weight percentage of each component is as follows: 25-40% of epoxy resin, 25-40% of polyester resin, 10-30% of auxiliary agent, 10-30% of filler, 0.5-10% of pigment and 0.5-10% of fire retardant.
However, the existing powder coatings have complex formula and poor corrosion resistance. Moreover, when high-temperature gas or fluid needs to be transported, the requirement on the flame retardant property of the coating is high, the conventional powder coating has little attention on the flame retardant property, and cannot obtain a satisfactory flame retardant effect, or the obtained powder coating has poor comprehensive performance only by paying attention to the flame retardant effect.
Disclosure of Invention
In view of the above problems, the object of the present invention is to provide a powder coating, which is corrosion resistant, weather resistant and flame retardant by formulation of preferably polyester resin.
The invention provides a corrosion-resistant weather-resistant flame-retardant polyester resin for powder coating, which has the following technical scheme that the raw materials comprise the following components in parts by weight: 102-138 parts of terephthalic acid, 26-38 parts of fluorine-containing dicarboxylic acid, 79-108 parts of isophthalic acid, 56-78 parts of neopentyl glycol, 20-28 parts of propylene glycol and 22-30 parts of fluorine-containing dihydric alcohol.
Preferably 108 to 130 parts of terephthalic acid, 29 to 36 parts of fluorine-containing dicarboxylic acid, 84 to 102 parts of isophthalic acid, 60 to 70 parts of neopentyl glycol, 22 to 26 parts of propylene glycol and 24 to 28 parts of fluorine-containing diol.
Wherein the fluorine-containing dicarboxylic acid comprises one or more of 2,6-difluoro-terephthalic acid, 2,5-difluoro-terephthalic acid, 2,3,6-trifluoro-terephthalic acid, preferably 2,6-difluoro-terephthalic acid.
Wherein, the fluorine-containing dihydric alcohol comprises one or more of 2,2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, preferably 2,2,3,3-tetrafluoro-1,4-butanediol.
Wherein the raw material of the polyester resin also comprises deoxybenzoin, and the content is 18-66 parts, preferably 20-50 parts.
The deoxybenzoin is 1,2-bis [4- (2-hydroxyethoxy) phenyl ] ethanone, and the structural formula is as follows:
wherein the raw material of the polyester resin also comprises a catalyst, the catalyst is selected from titanium catalysts, preferably tetrabutyl titanate, and the content of the catalyst is 0.001-0.1mol, preferably 0.01-0.05mol.
The invention also provides a preparation method of the polyester resin, which comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and optional deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula ratio, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours to discharge 95% of esterification water, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
The invention also provides a powder coating, which is prepared by respectively weighing the polyester resin, TGIC, a flatting agent, titanium dioxide, a filler and benzoin according to a certain proportion, uniformly mixing, melting by a screw extruder, respectively extruding, tabletting and crushing, and then crushing and sieving the tablets.
Wherein the weight ratio of the polyester resin, the TGIC, the leveling agent, the titanium dioxide, the filler and the benzoin is 100-300.
Wherein, the filler comprises one or more of barium sulfate, calcium carbonate, talcum powder and mica, and barium sulfate and calcium carbonate are preferred.
The invention also provides a coating, which is prepared by spraying the powder coating on a metal plate with the thickness of 0.5-1.0mm by using an electrostatic spray gun, wherein the thickness of the coating is 40-100 mu m, and curing for 10min at 200 ℃.
Compared with the prior art, the corrosion-resistant weather-resistant flame-retardant powder coating has the following beneficial effects:
(1) The polyester resin is prepared by adding the fluorine-containing dibasic acid and the dihydric alcohol, the fluorine-containing dibasic acid and the dihydric alcohol have unique C-F bonds, strong bond energy and short bond length, and the fluorine element has unique stability, so that the obtained fluorine-containing polyester resin has excellent corrosion resistance, weather resistance, stain resistance, self-cleaning property and the like. In addition, the invention comprehensively uses the fluorine-containing dibasic acid, the dihydric alcohol and other dibasic acids, reduces the cost of adding the fluorine element into the polyester resin, and simultaneously furthest retains the advantage of the fluorine element.
(2) Fluorine element has a certain flame retardant effect, but can only achieve the flame retardant effect of V1, if a certain amount of flame retardant is added, the flame retardant effect of polyester resin can be further improved, but the addition mode of the flame retardant and the polyester resin have the problem of compatibility, and the smoothness of the obtained coating often has a problem after the coating is prepared into powder coating and cured.
During the course of the test, the inventors realized that it is possible to add a copolymerizable flame retardant monomer to obtain an intrinsically flame retardant polyester resin, to obtain a flame retardant grade V0 polyester resin, and not to affect the flatness of the coating.
However, in the course of the test, the inventors have also found that, because of the particularity of fluorine element, although the corrosion resistance and the like of the polyester resin can be improved, the glass transition temperature of the polyester resin is lowered, which is probably because the fluorine-containing diol or the fluorine-containing dibasic acid has a regular destruction of the structure of the polyester resin and the fluorine element has a self-lubricating effect, resulting in an improvement in the flexibility of the polyester resin and thus a reduction in the glass transition temperature.
However, such a decrease in glass transition temperature leads to a decrease in storage stability of the powder coating, and is disadvantageous for storage of the powder coating. Through a plurality of tests, the inventor unexpectedly finds that the copolyester added with the flame-retardant comonomer deoxybenzoin can improve the flame-retardant property of the polyester resin and can effectively solve the problem of reduction of the glass transition temperature, thereby completing the invention.
The deoxybenzoin contains rigid benzene rings, so that the thermal property of the polyester resin can be improved to a certain extent, but the content of the deoxybenzoin is not too high, otherwise, the content of fluorine element can be diluted, and the corrosion resistance of the powder coating is influenced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a corrosion-resistant weather-resistant flame-retardant polyester resin for powder coating, which has the following technical scheme that the raw materials comprise the following components in parts by weight: 102-138 parts of terephthalic acid, 26-38 parts of fluorine-containing dicarboxylic acid, 79-108 parts of isophthalic acid, 56-78 parts of neopentyl glycol, 20-28 parts of propylene glycol and 22-30 parts of fluorine-containing dihydric alcohol.
Preferably 108 to 130 parts of terephthalic acid, 29 to 36 parts of fluorine-containing dicarboxylic acid, 84 to 102 parts of isophthalic acid, 60 to 70 parts of neopentyl glycol, 22 to 26 parts of propylene glycol and 24 to 28 parts of fluorine-containing diol.
Wherein the fluorine-containing dicarboxylic acid comprises one or more of 2,6-difluoro-terephthalic acid, 2,5-difluoro-terephthalic acid, 2,3,6-trifluoro-terephthalic acid, preferably 2,6-difluoro-terephthalic acid.
Wherein, the fluorine-containing dihydric alcohol comprises one or more of 2,2,3,3-tetrafluoro-1,4-butanediol and 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, and 2,2,3,3-tetrafluoro-1,4-butanediol is preferred.
Wherein the raw material of the polyester resin also comprises deoxybenzoin, and the content is 18-66 parts, preferably 20-50 parts.
The deoxybenzoin is 1,2-bis [4- (2-hydroxyethoxy) phenyl ] ethanone, and the structural formula is as follows:
wherein the raw material of the polyester resin also comprises a catalyst, the catalyst is selected from titanium catalysts, preferably tetrabutyl titanate, and the content of the catalyst is 0.001-0.1mol, preferably 0.01-0.05mol.
The invention also provides a preparation method of the polyester resin, which comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and optional deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula ratio, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours to discharge 95% of esterification water, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
The invention also provides a powder coating, which is prepared by respectively weighing the polyester resin, TGIC, a flatting agent, titanium dioxide, a filler and benzoin according to a certain proportion, uniformly mixing, melting by a screw extruder, respectively extruding, tabletting and crushing, and then crushing and sieving the tablets.
Wherein the weight ratio of the polyester resin, the TGIC, the leveling agent, the titanium dioxide, the filler and the benzoin is 100-300.
Wherein, the filler comprises one or more of barium sulfate, calcium carbonate, talcum powder and mica, and barium sulfate and calcium carbonate are preferred.
The invention also provides a coating, which is prepared by spraying the powder coating on a metal plate with the thickness of 0.5-1.0mm by using an electrostatic spray gun, wherein the thickness of the coating is 40-100 mu m, and curing for 10min at 200 ℃.
Example 1
The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating comprises the following raw materials in molar ratio: 119.6g of terephthalic acid, 32.3g of 2, 6-difluoro-terephthalic acid, 93.0g of isophthalic acid, 66.7g of neopentyl glycol, 24.3g of propylene glycol, 25.9g of 2, 3-tetrafluoro-1,4-butanediol, 22.8g of deoxybenzoin; the catalyst is tetrabutyl titanate 0.03mol.
The preparation method of the polyester resin comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula amount, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours until 95% of the esterification water is discharged, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
Example 2
The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating comprises the following raw materials in molar ratio: 119.6g of terephthalic acid, 32.3g of 2, 6-difluoro-terephthalic acid, 93.0g of isophthalic acid, 66.7g of neopentyl glycol, 24.3g of propylene glycol, 25.9g of 2, 3-tetrafluoro-1,4-butanediol, 36.5g of deoxybenzoin; the catalyst is tetrabutyl titanate 0.03mol.
The preparation method of the polyester resin comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula ratio, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours to discharge 95% of esterification water, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
Example 3
The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating comprises the following raw materials in molar ratio: 119.6g of terephthalic acid, 32.3g of 2, 6-difluoro-terephthalic acid, 93.0g of isophthalic acid, 66.7g of neopentyl glycol, 24.3g of propylene glycol, 25.9g of 2, 3-tetrafluoro-1,4-butanediol, 41.1g of deoxybenzoin; the catalyst is tetrabutyl titanate 0.03mol.
The preparation method of the polyester resin comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and deoxybenzoin according to the formula ratio into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating to melt at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula amount, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours until 95% of the esterification water is discharged, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
Comparative example 1
The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating comprises the following raw materials in molar ratio: 119.6g of terephthalic acid, 32.3g of 2, 6-difluoro-terephthalic acid, 93.0g of isophthalic acid, 66.7g of neopentyl glycol, 24.3g of propylene glycol, 25.9g of 2, 3-tetrafluoro-1,4-butanediol; the catalyst is tetrabutyl titanate 0.03mol.
The preparation method of the polyester resin comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol and fluorine-containing dihydric alcohol in a formula ratio into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula amount, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours until 95% of the esterification water is discharged, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
Comparative example 2
The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating comprises the following raw materials in molar ratio: 132.9g of terephthalic acid, 32.3g of 2, 6-difluoro-terephthalic acid, 99.7g of isophthalic acid, 66.7g of neopentyl glycol, 24.3g of propylene glycol, 25.9g of 2, 3-tetrafluoro-1,4-butanediol, 68.5g of deoxybenzoin; the catalyst is tetrabutyl titanate 0.04mol.
The preparation method of the polyester resin comprises the following steps:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and optional deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula ratio, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours to discharge 95% of esterification water, and enabling the acid value to reach 12-15mgKOH/g;
(3) Then cooling to 200-210 ℃, adding m-phthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, carrying out vacuum polycondensation for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500 mPas.
The obtained polyester is tested, and the tested performances comprise an acid value, a softening point, a glass transition temperature, a melt viscosity and a flame retardant property, wherein the acid value test is carried out according to the standard of GB/T6743-2008, the softening point test is carried out according to the standard of GB/T27808-2011, the glass transition temperature test is carried out according to the standard of GB/T19466.2-2004, the melt viscosity is detected according to the standard of GB/T9751.1-2008, the flame retardant property is carried out according to the standard of GB/T2408-2008, and the test result is shown in Table 1.
Table 1: composition and Properties of polyester resin
The polyester resins prepared in examples 1 to 3 and comparative examples 1 to 2 were marked as polyester 1 to 5, and the corresponding polyester resins were weighed and mixed with TGIC, leveling agent, titanium dioxide, barium sulfate, calcium carbonate and benzoin according to the ratio in Table 2, melted by a screw extruder, extruded, tabletted and crushed respectively, and then the tabletted materials were pulverized and sieved to prepare powder coatings. The powder coating is sprayed on a derusting and deoiling metal plate with the thickness of 0.8mm by an electrostatic spray gun, the thickness of the coating is 60 mu m, and the powder coating is solidified at the temperature of 200 ℃/10 min.
Then testing the appearance, hardness, heat resistance and corrosion resistance of the coating, and visually observing whether the cured coating is flat or not, whether folds, air holes and the like exist or not by using the appearance; the hardness is tested according to the GB/T6739-2006 standard, and a pencil is used for testing whether the coating can be marked or scratched; the heat resistance is tested according to the standard GB/T1735-1979 after baking in an oven at 250 ℃; the salt spray resistance of the coating is mainly tested according to the GB/T1771-2007 standard, a continuous spraying mode is adopted, the solution is 5% NaCl solution, the test temperature is 35 +/-2 ℃, and related test results are shown in Table 2.
TABLE 2 coating Properties formed by powder coatings
Those skilled in the art will appreciate that the above-described embodiments are merely a few, and not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Claims (11)
1. The corrosion-resistant weather-resistant flame-retardant polyester resin for the powder coating is characterized by comprising the following raw materials in parts by weight: 102-138 parts of terephthalic acid, 26-38 parts of fluorine-containing dicarboxylic acid, 79-108 parts of isophthalic acid, 56-78 parts of neopentyl glycol, 20-28 parts of propylene glycol, 22-30 parts of fluorine-containing dihydric alcohol and 18-66 parts of deoxybenzoin;
the fluorine-containing dicarboxylic acid comprises one or more of 2,6-difluoro-terephthalic acid, 2,5-difluoro-terephthalic acid, 2,3,6-trifluoro-terephthalic acid;
the fluorine-containing dihydric alcohol comprises one or more of 2,2,3,3-tetrafluoro-1,4-butanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol.
2. The polyester resin according to claim 1, wherein the fluorine-containing dicarboxylic acid is 2,6-difluoro-terephthalic acid.
3. The polyester resin according to claim 1, wherein the fluorine-containing diol is 2,2,3,3-tetrafluoro-1,4-butanediol.
4. The polyester resin as claimed in claim 1, wherein the deoxybenzoin content is 20 to 50 parts.
5. The polyester resin according to claim 1, wherein the raw material of the polyester resin further comprises a catalyst selected from titanium-based catalysts, and the content of the catalyst is 0.001 to 0.1mol.
6. The polyester resin according to claim 5, wherein the catalyst is selected from tetrabutyl titanate and the catalyst content is 0.01 to 0.05mol.
7. A method for preparing the polyester resin according to any one of claims 1 to 6, comprising the steps of:
(1) Adding neopentyl glycol, propylene glycol, fluorine-containing dihydric alcohol and deoxybenzoin in formula amount into a reaction vessel provided with a stirring and refluxing condenser pipe, mixing and stirring, and heating and melting at 100-140 ℃;
(2) Continuously heating to 150-180 ℃, adding terephthalic acid, fluorine-containing dicarboxylic acid and a catalyst according to the formula amount, introducing nitrogen, heating to 180-190 ℃, starting esterification reaction and distilling off generated esterification water, then gradually heating to 22-250 ℃, reacting for 5-10 hours to 95% of esterification water, and discharging, wherein the acid value reaches 12-15 mgKOH/g;
(3) Then cooling to 200-210 ℃, adding the isophthalic acid with the formula amount, continuously and gradually heating to 250-270 ℃, reacting until the acid value reaches 40-48mgKOH/g, vacuumizing and polycondensing for 6-10 hours, stopping the reaction when the acid value reaches 35-45mgKOH/g and the melt viscosity is 3500-5500mPa & s.
8. A powder coating, characterized in that, weigh the polyester resin of any claim 1-6 and TGIC, levelling agent, titanium pigment, filler, benzoin according to certain matching, mix, melt and extrude separately, slice, break with the screw extruder, then pulverize slice and sieve to make powder coating;
wherein the weight ratio of the polyester resin, the TGIC, the flatting agent, the titanium dioxide, the filler and the benzoin is (100-300).
9. The powder coating of claim 8, wherein the filler comprises one or more of barium sulfate, calcium carbonate, talc, and mica.
10. The powder coating of claim 9, wherein the filler comprises one or more of barium sulfate and calcium carbonate.
11. A coating obtained by spraying the powder coating according to any one of claims 8 to 10 onto a metal sheet having a thickness of 0.5 to 1.0mm by means of an electrostatic spray gun, the coating thickness being 40 to 100 μm and curing at 200 ℃ for 10 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923120A (en) * | 2013-01-11 | 2014-07-16 | 纳幕尔杜邦公司 | Deoxybenzoin fire retardation agent, composition containing deoxybenzoin fire retardation agent, product containing deoxybenzoin fire retardation agent, and method for reducing combustibility of polymer material by using deoxybenzoin fire retardation agent |
| CN104530408A (en) * | 2015-01-08 | 2015-04-22 | 黄山市向荣新材料有限公司 | Polyester resin for ultra-weather-proof powder coating, powder coating with resin and preparing method for powder coating |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
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- 2021-05-08 CN CN202110499462.2A patent/CN113150658B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923120A (en) * | 2013-01-11 | 2014-07-16 | 纳幕尔杜邦公司 | Deoxybenzoin fire retardation agent, composition containing deoxybenzoin fire retardation agent, product containing deoxybenzoin fire retardation agent, and method for reducing combustibility of polymer material by using deoxybenzoin fire retardation agent |
| CN104530408A (en) * | 2015-01-08 | 2015-04-22 | 黄山市向荣新材料有限公司 | Polyester resin for ultra-weather-proof powder coating, powder coating with resin and preparing method for powder coating |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
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