CN112521838A - Extinction transparent polyester resin composition and preparation method and application thereof - Google Patents
Extinction transparent polyester resin composition and preparation method and application thereof 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
- C08G63/02—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
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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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- 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
- 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
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a delustering transparent polyester resin composition, a preparation method and application thereof, wherein the delustering transparent polyester resin composition comprises a high-acid-value carboxyl-terminated polyester resin A and a low-acid-value carboxyl-terminated polyester resin B, the high-acid-value carboxyl-terminated polyester resin A and the low-acid-value carboxyl-terminated polyester resin B have the properties of higher glass transition temperature, lower hydroxyl value, proper acid value, melt viscosity, reactivity and the like, and the formed polyester resin composition has higher transparency. The powder coating prepared from the extinction transparent polyester resin composition has high transparency after being cured, and has good leveling property, mechanical property and weather resistance.
Description
Technical Field
The invention relates to the technical field of polyester resin, in particular to a delustering transparent polyester resin composition and a preparation method and application thereof.
Background
In the coating of automobile hubs or metal silver paint and the like, in order to protect metal substrates or silver paint, prevent corrosion, improve the performances of weather resistance, water resistance, alkali resistance, yellowing resistance, scratch resistance and the like, and improve the fullness and decoration of a coating film, transparent finishing paint needs to be sprayed for finishing. Overprint varnishes, commonly known as gloss oils, are commonly used to enhance the gloss finish of finished products and are high gloss coatings, typically single component polyester, polyurethane or acrylic coatings. In recent years, due to the change of aesthetic concepts of people and the environmental protection trend of 'changing paint into powder', the market has seen the demand of matte transparent finishing powder coating.
Chinese patent CN103131308A provides a high-low acid value bi-component carboxyl-terminated polyester resin composition for an ultra-weather-resistant dry-mixed extinction powder coating, the composition is a high-low acid value bi-component composition consisting of a high-acid value carboxyl-terminated polyester resin A and a low-acid value carboxyl-terminated polyester resin B, and the composition is matched and combined with pigments and fillers to prepare a common ultra-weather-resistant powder coating; in addition, because the two polyester resins in the composition have large structural difference, the two components may have certain incompatibility after being prepared into a powder coating, so that the coating film has poor transparency. Chinese patent CN106046711A discloses a dry-mixed delustering polyester resin composition for heat transfer printing powder coating, which is mainly used for heat transfer printing powder coating, needs to be added with more heat transfer printing auxiliary agents and low-temperature curing auxiliary agents, is mainly used for low-temperature curing heat transfer printing powder coating, does not consider the application in the application field of matte transparent finishing, and possibly has the problem of poor transparency of resin and coating. Other prior art has the problems of poor transparency of polyester, poor transparency of matte coatings after dry mixing and extinction, poor weather resistance and mechanical property of coating films and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a delustering transparent polyester resin composition, and a coating formed by curing the prepared powder coating is high in transparency and has good leveling property, mechanical property and weather resistance.
The invention also provides a preparation method and application of the extinction transparent polyester resin composition.
Specifically, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a mat transparent polyester resin composition comprising a high acid value carboxyl-terminated polyester resin A and a low acid value carboxyl-terminated polyester resin B, wherein,
(1) the acid value of the high-acid-value carboxyl-terminated polyester resin A is 48-54 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, the glass transition temperature is 60-70 ℃, the melt viscosity at 200 ℃ is 4000-6500 mPa & s, the reactivity at 180 ℃ is 50-150 s, and the number average molecular weight is 3000-6000;
(2) the low-acid-value carboxyl-terminated polyester resin B has an acid value of 18-24 mgKOH/g, a hydroxyl value of less than 5mgKOH/g, a glass transition temperature of 60-70 ℃, a melt viscosity of 4000-6500 mPa · s at 200 ℃, a reactivity of 250-350 s at 180 ℃, and a number average molecular weight of 3000-6000.
Preferably, the high acid value carboxyl-terminated polyester resin A is mainly prepared by polycondensation of the following raw materials in percentage by weight:
polyol: 33 to 43 percent
Polybasic acid: 45 to 55 percent
Acid hydrolysis agent: 5 to 15 percent
Esterification catalyst: 0.01 to 0.15 percent
Wherein the ratio r1 of alcoholic acid to carboxyl acid in the polyhydric alcohol is 1.10-1.14: 1.
preferably, the low-acid-value carboxyl-terminated polyester resin B is mainly prepared by polycondensation of the following raw materials in percentage by weight:
polyol: 35 to 45 percent
Polybasic acid: 45 to 55 percent
Acid hydrolysis agent: 5 to 15 percent
Esterification catalyst: 0.01 to 0.15 percent
Wherein the ratio r1 of alcoholic acid to carboxyl acid in the polyhydric alcohol is 1.16-1.20: 1.
preferably, the total number of types of synthetic raw materials of the high acid value carboxyl-terminated polyester resin A is more than or equal to 5.
Preferably, the total number of types of synthetic raw materials of the low acid value carboxyl-terminated polyester resin B is more than or equal to 5.
Preferably, the absolute value of the difference between the total number of synthetic raw material types of the high acid value carboxyl-terminated polyester resin A and the low acid value carboxyl-terminated polyester resin B is less than or equal to 2.
Preferably, the raw materials for preparing the high acid value carboxyl-terminated polyester resin A and the low acid value carboxyl-terminated polyester resin B respectively also comprise transparent modifying monomers.
Preferably, the weight percentage of the transparent modified monomer in the raw materials for preparing the high-acid-value carboxyl-terminated polyester resin A or the low-acid-value carboxyl-terminated polyester resin B is 0-8%.
Preferably, the transparent modifying monomer comprises at least one of epsilon-caprolactone or 6-hydroxycaproic acid.
Preferably, the polyol comprises at least one of neopentyl glycol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, ditrimethylolpropane, and pentaerythritol.
The polybasic acid comprises at least one of isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, hydrogenated bisphenol A, hexahydrophthalic anhydride, succinic acid, adipic acid and sebacic acid.
The acidolysis agent comprises at least one of isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, hydrogenated bisphenol A, hexahydrophthalic anhydride, succinic acid, adipic acid, sebacic acid, trimellitic anhydride and pyromellitic anhydride.
The esterification catalyst comprises at least one of a tin catalyst, a germanium catalyst and a titanium catalyst, wherein the tin catalyst comprises at least one of monobutyl tin oxide, tin oxalate and monobutyl dihydroxy tin chloride; the germanium-based catalyst comprises germanium dioxide; the titanium catalyst comprises at least one of tetrabutyl titanate, tetraisopropyl titanate, titanium dioxide and organic titanium chelate.
The second aspect of the present invention provides a process for preparing a mat transparent polyester resin composition, comprising the steps of:
preparation of high acid value carboxyl-terminated polyester resin a:
1) mixing polyalcohol, polybasic acid and esterification catalyst, carrying out esterification reaction, and vacuumizing to obtain an esterification product;
2) adding an acidolysis agent into the esterification product for acidolysis reaction to obtain an acidolysis product;
3) carrying out vacuum polycondensation on the acidolysis product until the acid value is 48-54 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s, so as to obtain a high-acid-value carboxyl-terminated polyester resin A;
preparation of low acid value carboxyl-terminated polyester resin B:
1) mixing polyalcohol, polybasic acid and an esterification catalyst, and carrying out esterification reaction to obtain an esterification product;
2) adding an acidolysis agent into the esterification product for acidolysis reaction to obtain an acidolysis product;
3) and (3) carrying out vacuum polycondensation on the acidolysis product until the acid value is 18-24 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s, thus obtaining the low-acid-value carboxyl-terminated polyester resin B.
Preferably, in the step 1) of preparing the high acid value carboxyl-terminated polyester resin A, the esterification reaction is carried out until the acid value is 5 to 15mgKOH/g, and the vacuum pumping is carried out until the acid value is 2 to 8 mgKOH/g.
Preferably, in the step 1) for preparing the high acid value carboxyl-terminated polyester resin a, the esterification reaction is carried out by the following steps: after the materials are added, the temperature is raised to 180-190 ℃ within 1 hour, then raised to 200-210 ℃ within 2 hours, the temperature is kept for 1-1.5 hours, the temperature is raised to 220-230 ℃ within 1 hour, the temperature is raised to 240-250 ℃ within 2 hours, and the temperature is kept for 2-3 hours.
Preferably, in the step 1) of preparing the high acid value carboxyl-terminated polyester resin A, the vacuum degree is pumped to-0.088 to-0.098 MPa.
Preferably, in the step 2) of preparing the high acid value carboxyl-terminated polyester resin A, acid hydrolysis reaction is carried out until the acid value is 58-64 mgKOH/g.
Preferably, in the step 2) of preparing the high acid value carboxyl-terminated polyester resin A, the temperature of the acidolysis reaction is 230-240 ℃; the acidolysis reaction time is 2-4 h.
Preferably, in the step 3) for preparing the high acid value carboxyl-terminated polyester resin A, the vacuum degree of the vacuum polycondensation reaction is-0.088 to-0.098 MPa.
Preferably, in the step 3) for preparing the high acid value carboxyl-terminated polyester resin A, the vacuum polycondensation reaction time is 1-3 h.
Preferably, in the step 1) of preparing the low acid value carboxyl-terminated polyester resin B, the esterification reaction is carried out until the acid value is 5-15 mgKOH/g, and the vacuum pumping is carried out until the acid value is 2-6 mgKOH/g.
Preferably, in the step 1) of preparing the low acid value carboxyl-terminated polyester resin B, the esterification reaction is performed by: after the materials are added, the temperature is raised to 180-190 ℃ within 1 hour, then raised to 200-210 ℃ within 2 hours, the temperature is kept for 1-1.5 hours, the temperature is raised to 220-230 ℃ within 1 hour, the temperature is raised to 240-250 ℃ within 2 hours, and the temperature is kept for 2-3 hours.
Preferably, in the step 1) of preparing the low acid value carboxyl-terminated polyester resin B, the vacuum degree is pumped to-0.088 to-0.098 MPa.
Preferably, in the step 2) of preparing the low acid value carboxyl-terminated polyester resin B, acid hydrolysis reaction is carried out until the acid value is 30-36 mgKOH/g.
Preferably, in the step 2) of preparing the low-acid-value carboxyl-terminated polyester resin B, the temperature of the acidolysis reaction is 230-240 ℃; the acidolysis reaction time is 2-4 h.
Preferably, in the step 3) for preparing the low acid value carboxyl-terminated polyester resin B, the vacuum degree of the vacuum polycondensation reaction is-0.088 to-0.098 MPa.
Preferably, in the step 3) for preparing the low-acid-value carboxyl-terminated polyester resin B, the vacuum polycondensation reaction time is 1-3 h.
In a third aspect of the present invention, there is provided a dry-mix matte powder coating comprising the above matte transparent polyester resin composition.
The dry-mixed extinction powder coating is prepared by dry-mixing a component I and a component II, wherein the component I comprises the polyester resin high-acid-value carboxyl-terminated polyester resin A, a curing agent and an auxiliary agent, and the component II comprises the polyester resin low-acid-value carboxyl-terminated polyester resin B, the curing agent and the auxiliary agent.
The mass ratio of the component I to the component II is 1-2: 1.
the curing agent comprises triglycidyl isocyanurate (TGIC), Hydroxyalkylamide (HAA) or polyglycidyl benzoate (diglycidyl terephthalate, triglycidyl trimellitate or triglycidyl trimesate and mixtures thereof).
The auxiliary agent comprises a high-transparency leveling agent, benzoin, an ultraviolet light absorber and the like.
In addition, the powder coating can be used for coating the surface of a workpiece (such as a hardware workpiece) to form a protective coating. Therefore, the invention also provides a workpiece, and a coating formed by the dry-mixed extinction powder coating is attached to the surface of the workpiece.
The workpiece comprises an automobile hub.
The invention has the beneficial effects that:
1. the high acid value carboxyl-terminated polyester resin A and the low acid value carboxyl-terminated polyester resin B have the properties of higher glass transition temperature, lower hydroxyl value, proper acid value, melt viscosity, reactivity and the like, and the formed polyester resin composition has higher transparency.
2. The powder coating prepared from the polyester resin A with high acid value and the polyester resin B with low acid value and carboxyl end groups has higher glass transition temperature and good storage stability, and the coating after spraying, baking and curing has high transparency, good leveling property, mechanical property and weather resistance.
3. The dry-mixed extinction matte transparent powder coating prepared by matching the polyester resin A with high acid value and the polyester resin B with low acid value and carboxyl end group with poly-glycidyl benzoate has the same excellent mechanical property, weather resistance and transparency as the powder coating prepared by matching TGIC.
Detailed Description
The present invention will be described in further detail with reference to examples.
The invention provides a delustering transparent polyester resin composition, which contains a high-acid-value carboxyl-terminated polyester resin A and a low-acid-value carboxyl-terminated polyester resin B. By way of example, the high acid number carboxyl-terminated polyester resin a may be prepared by polycondensation of the following raw materials as shown in table 1:
TABLE 1
The preparation method of the high acid value carboxyl-terminated polyester resin A of the embodiment 1 to 5 comprises the following steps:
1) adding polyol into a 5L reaction kettle, heating until the materials are molten, adding polybasic acid and an esterification catalyst, and carrying out esterification reaction under the condition of isolating oxygen. More specifically, after polybasic acid and an esterification catalyst are added into molten polyol, the temperature is raised to 180 ℃ within 1 hour, then raised to 210 ℃ within 2 hours, the temperature is kept for 1.5 hours, the temperature is raised to 220 ℃ within 1 hour, the temperature is raised to 240-250 ℃ within 2 hours, the temperature is kept for 3 hours, the reaction is carried out until the acid value is 6-12 mgKOH/g, then the vacuum pumping is carried out until the pressure is-0.098 MPa, and the acid value is 2-8 mgKOH/g, so that an esterification product is obtained.
2) And under the condition of isolating oxygen, adding an acidolysis agent into the esterification product, carrying out acidolysis reaction, and reacting at about 235 ℃ for 2-3 h until the acid value is 58-64 mgKOH/g to obtain the acidolysis product.
3) Vacuumizing (vacuum degree of-0.098 MPa) for 1-3 h, and reacting until the acid value is 48-54 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s to obtain the high-acid-value carboxyl-terminated polyester resin A.
Wherein the transparent modifying monomers of examples 4 and 5 are added at step 1) together with the polyol.
The preparation method of the high-acid-value carboxyl-terminated polyester resin in the comparative examples 6-7 by adopting the conventional super-weather-resistant dry-mixed extinction polyester resin specifically comprises the following steps:
adding the polyhydric alcohols with the proportion shown in the table 1 into a 5L reaction kettle, and heating until the materials are melted; sequentially adding polybasic acid and an esterification catalyst, introducing nitrogen to continue heating reaction, starting to generate and distilling off esterification water at about 180 ℃, gradually heating to 240 ℃, reacting for 5-10 h to 95% of esterification water, and discharging, wherein the acid value reaches 6-20 mgKOH/g; and then adding an acidolysis agent, reacting for 1-3 h, vacuumizing and polycondensing for about 1-5 h when the acid value is 55-62 mgKOH/g, and stopping the reaction when the acid value reaches 45-55 mgKOH/g.
The properties of the high acid value carboxyl-terminated polyester resins A of examples 1 to 5 and comparative examples 6 to 7 are shown in Table 2 below:
TABLE 2
Note: the acid number, viscosity, glass transition temperature and reactivity were tested according to T/GDTL 004-; hydroxyl number was tested according to GB/T12008.3-2009; testing the light transmittance according to GB/T2410-2008, placing a sample in a standard cuvette, heating to melt, vacuumizing and removing bubbles, and then testing; the same applies below.
The low acid number carboxyl-terminated polyester resin B can be prepared by polycondensation of the following raw materials as shown in table 3:
TABLE 3
The preparation method of the low-acid-value carboxyl-terminated polyester resin B in the embodiment 8-12 comprises the following steps:
1) adding polyol into a 5L reaction kettle, heating until the materials are molten, adding polybasic acid and an esterification catalyst, and carrying out esterification reaction under the condition of isolating oxygen. More specifically, after polybasic acid and an esterification catalyst are added into molten polyol, the temperature is raised to 180 ℃ within 1 hour, then raised to 210 ℃ within 2 hours, the temperature is kept for 1.5 hours, the temperature is raised to 220 ℃ within 1 hour, the temperature is raised to 240-250 ℃ within 2 hours, the temperature is kept for 3 hours, the reaction is carried out until the acid value is 6-10 mgKOH/g, then the vacuum is pumped to-0.098 MPa, and the acid value is 2-6 mgKOH/g, so that an esterification product is obtained.
2) And under the condition of isolating oxygen, adding an acidolysis agent into the esterification product, carrying out acidolysis reaction, and reacting at 235 ℃ for 2-3 h until the acid value is 30-36 mgKOH/g, thereby obtaining the acidolysis product.
3) Vacuumizing (vacuum degree of-0.098 MPa) for 1-3 h, and reacting until the acid value is 18-24 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s to obtain the low-acid-value carboxyl-terminated polyester resin B.
Wherein the transparent modifying monomers of examples 11 and 12 are added together with the polyol at step 1).
The low-acid-value carboxyl-terminated polyester resin of comparative examples 13 to 14 is prepared by a conventional method for preparing a super-weather-resistant dry-mixed extinction polyester resin, and specifically comprises the following steps:
adding the polyhydric alcohols with the proportion shown in the table 3 into a 5L reaction kettle, heating and raising the temperature until the materials are melted; sequentially adding polybasic acid and an esterification catalyst, introducing nitrogen, continuing to perform a heating reaction, starting to generate and distilling off esterification water at about 180 ℃, gradually heating to 240 ℃, reacting for 5-10 h to 95% of esterification water, and discharging, wherein the acid value reaches 6-15 mgKOH/g; and then adding an acidolysis agent, reacting for 1-3 h, vacuumizing and polycondensing for about 1-5 h when the acid value reaches 30-39 mgKOH/g, and stopping the reaction when the acid value reaches 17-25 mgKOH/g.
The properties of the low acid value carboxyl-terminated polyester resins B of examples 8 to 12 and comparative examples 13 to 14 are shown in Table 4 below:
TABLE 4
Preparation and performance test of the powder coating:
1. the high acid value carboxyl-terminated polyester resin A and the low acid value carboxyl-terminated polyester resin B are respectively weighed and uniformly mixed with curing agent TGIC, flatting agent GLP588 and benzoin according to the proportion of the following table 5 (note: if no special description exists, the component units in the table 5 are g), the mixture is melted, extruded, tableted and crushed by a screw extruder, then the tablet is crushed and sieved to obtain the component I and the component II of the powder coating, the component I and the component II of the powder coating are uniformly mixed according to the weight ratio of 1:1 according to the table 6, and the dry-mixed extinction powder coating of the embodiment 15-19 and the comparative example 20-21 is prepared.
TABLE 5
TABLE 6
2. The powder coatings prepared in examples 15 to 19 and comparative examples 20 to 21 were electrostatically sprayed on surface-treated iron plates and standard thin optical glass plates and cured at 200 ℃ for 10min to give powder coatings of about 60 μm thickness, and then subjected to the following performance tests, the results of which are shown in Table 7:
TABLE 7
Note: visual inspection of the appearance of the coating film; testing the gloss, the bending, the impact and the xenon lamp aging according to T/GDTL 004-; hydroxyl number was tested according to GB/T12008.3-2009; the light transmittance is tested according to GB/T2410-2008.
As can be seen from tables 2 and 4, the high acid value carboxyl-terminated polyester resin a and the low acid value carboxyl-terminated polyester resin B of the present invention have high transparency, low hydroxyl value, suitable reactivity, and high glass transition temperature. As can be seen from Table 7, compared with the conventional super-weather-resistant dry-mixed extinction polyester resin, the powder coating prepared from the polyester resin composition has higher surface morphology (orange peel) grade, better coating leveling property, high extinction coating transparency, excellent weather resistance and mechanical properties, and delicate surface of the extinction coating, and is more suitable for matte transparent dry-mixed extinction powder coatings.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A mat transparent polyester resin composition characterized by: comprises a high acid value carboxyl-terminated polyester resin A and a low acid value carboxyl-terminated polyester resin B, wherein,
(1) the acid value of the high-acid-value carboxyl-terminated polyester resin A is 48-54 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, the glass transition temperature is 60-70 ℃, the melt viscosity at 200 ℃ is 4000-6500 mPa & s, the reactivity at 180 ℃ is 50-150 s, and the number average molecular weight is 3000-6000;
(2) the low-acid-value carboxyl-terminated polyester resin B has an acid value of 18-24 mgKOH/g, a hydroxyl value of less than 5mgKOH/g, a glass transition temperature of 60-70 ℃, a melt viscosity of 4000-6500 mPa · s at 200 ℃, a reactivity of 250-350 s at 180 ℃, and a number average molecular weight of 3000-6000.
2. The matted transparent polyester resin composition according to claim 1, wherein: the high-acid-value carboxyl-terminated polyester resin A is mainly prepared by polycondensation of the following raw materials in percentage by weight:
polyol: 33 to 43 percent
Polybasic acid: 45 to 55 percent
Acid hydrolysis agent: 5 to 15 percent
Esterification catalyst: 0.01 to 0.15 percent
The ratio of the amount of hydroxyl groups in the polyol to the amount of carboxyl groups in the polyacid is 1.10 to 1.14: 1.
3. the matted transparent polyester resin composition according to claim 1, wherein: the low-acid-value carboxyl-terminated polyester resin B is mainly prepared by polycondensation of the following raw materials in percentage by weight:
polyol: 35 to 45 percent
Polybasic acid: 45 to 55 percent
Acid hydrolysis agent: 5 to 15 percent
Esterification catalyst: 0.01 to 0.15 percent
The ratio of the amount of hydroxyl groups in the polyol to the amount of carboxyl groups in the polyacid is 1.16 to 1.20: 1.
4. a mat transparent polyester resin composition according to any one of claims 1 to 3, characterized in that: the total number of types of synthetic raw materials of the high-acid-value carboxyl-terminated polyester resin A is more than or equal to 5.
5. The matted transparent polyester resin composition according to claim 4, wherein: the total number of types of synthetic raw materials of the low-acid-value carboxyl-terminated polyester resin B is more than or equal to 5.
6. The matted transparent polyester resin composition according to claim 5, wherein: the absolute value of the difference between the total number of synthetic raw material types of the high acid value carboxyl-terminated polyester resin A and the low acid value carboxyl-terminated polyester resin B is less than or equal to 2.
7. A process for producing a mat transparent polyester resin composition according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
preparation of high acid value carboxyl-terminated polyester resin a:
1) mixing polyalcohol, polybasic acid and esterification catalyst, carrying out esterification reaction, and vacuumizing to obtain an esterification product;
2) adding an acidolysis agent into the esterification product for acidolysis reaction to obtain an acidolysis product;
3) carrying out vacuum polycondensation on the acidolysis product until the acid value is 48-54 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s, so as to obtain a high-acid-value carboxyl-terminated polyester resin A;
preparation of low acid value carboxyl-terminated polyester resin B:
1) mixing polyalcohol, polybasic acid and an esterification catalyst, and carrying out esterification reaction to obtain an esterification product;
2) adding an acidolysis agent into the esterification product for acidolysis reaction to obtain an acidolysis product;
3) and (3) carrying out vacuum polycondensation on the acidolysis product until the acid value is 18-24 mgKOH/g, the hydroxyl value is less than 5mgKOH/g, and the melt viscosity at 200 ℃ is 4000-6500 mPa & s, thus obtaining the low-acid-value carboxyl-terminated polyester resin B.
8. A dry-mixed extinction powder coating is characterized in that: a mat transparent polyester resin composition comprising the composition according to any one of claims 1 to 6.
9. The dry mix matte powder coating of claim 8, wherein: the dry-mixed extinction powder coating is prepared by dry-mixing a component I and a component II, wherein the component I comprises the polyester resin high-acid-value carboxyl-terminated polyester resin A, a curing agent and an auxiliary agent, and the component II comprises the polyester resin low-acid-value carboxyl-terminated polyester resin B, the curing agent and the auxiliary agent.
10. The utility model provides a hardware workpiece which characterized in that: the surface of the hardware workpiece is adhered with a coating layer formed by the dry-mixed extinction powder coating of claim 8 or 9.
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