CN108165144B - Hammer powder coating and preparation method thereof - Google Patents
Hammer powder coating and preparation method thereof Download PDFInfo
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- CN108165144B CN108165144B CN201711291549.0A CN201711291549A CN108165144B CN 108165144 B CN108165144 B CN 108165144B CN 201711291549 A CN201711291549 A CN 201711291549A CN 108165144 B CN108165144 B CN 108165144B
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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
- 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
- C08G63/02—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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- 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
- C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
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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
- C09D5/18—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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Abstract
The invention discloses a preparation method of hammer-line powder coating, which comprises the following steps: premixing carboxyl-terminated polyester resin, epoxy resin, a filler, a hammer agent, a pigment and a low-temperature curing accelerator for 6-9min, stirring to obtain a mixture M1, carrying out melt extrusion and tabletting on the mixture M1 to obtain a sheet material, and grinding and sieving the sheet material to obtain the hammer powder coating; wherein, the carboxyl-terminated polyester resin is prepared by the following method: mixing and melting polyol, polyalkyl organic silicon resin and an esterification catalyst, adding aromatic polybasic acid and fatty polybasic acid, then carrying out heat treatment, and then adding an acidolysis agent for end capping and depolymerization; finally, carrying out vacuum polycondensation to obtain the carboxyl-terminated polyester resin for the hammer powder coating, wherein the acid value is 10-25mgKOH/g in the heat treatment process. The hammer powder coating has a series of excellent performances of high stability, high heat resistance, aging resistance and the like; can keep the use effects of the paint such as beauty and the like for a long time.
Description
Technical Field
The invention relates to the field of powder coatings, in particular to a hammer-grained powder coating and a preparation method thereof.
Background
The powder coating has the advantages of environmental friendliness, low production cost, simple production process and the like, and the application range is wider and wider. The common thermosetting and thermoplastic powder coating is generally baked at the temperature of more than 180 ℃ and cured for about 20min, and the high curing temperature limits that the powder coating can only be applied to heat-resistant base materials such as metal and the like; in the field of heat-sensitive base materials, the curing temperature is too high, so that the heat-sensitive base material cannot be popularized. In addition, with the improvement of the living standard of people, the requirements on the living quality are also improved; the powder coating with the hammer effect can cover the defects of the base material, and is closer to the needs of the public in appearance. Therefore, the application of hammer powder coatings to various substrates is also a hot spot in the powder industry.
However, the prior preparation process of carboxyl-terminated polyester resin is complex and high in preparation cost, and the single production process further causes that the performance of the prepared powder coating is single and can not meet the application requirements of various substrate materials or fields. In addition, the powder coating prepared by the carboxyl-terminated polyester resin prepared by the traditional preparation process has poor weather resistance, such as a series of poor stability performances such as easy aging at high temperature, and the like, and particularly when the powder coating is used for preparing hammer-grained powder coating, the spraying effect, the service life and the aesthetic property of the coating are directly influenced.
Disclosure of Invention
The invention aims to provide a hammer tone powder coating and a preparation method thereof, wherein the hammer tone powder coating has simple production process, simple and easily-obtained raw materials and can be produced in batch; the hammer powder coating has a series of excellent performances such as high stability, high heat resistance, aging resistance and the like; can keep the use effects of the paint such as beauty and the like for a long time.
In order to achieve the above object, the present invention provides a method for preparing a hammer powder coating, the method comprising:
premixing carboxyl-terminated polyester resin, epoxy resin, a filler, a hammer agent, a pigment and a low-temperature curing accelerator for 6-9min, stirring to obtain a mixture M1, carrying out melt extrusion and tabletting on the mixture M1 to obtain a sheet material, and grinding and sieving the sheet material to obtain the hammer powder coating;
wherein the carboxyl-terminated polyester resin is prepared by the following method:
mixing and melting polyol, polyalkyl organic silicon resin and an esterification catalyst, adding aromatic polybasic acid and fatty polybasic acid, then carrying out heat treatment, and then adding an acidolysis agent for end capping and depolymerization; and finally, carrying out vacuum polycondensation to obtain the carboxyl-terminated polyester resin for the hammer tone powder coating, wherein the acid value in the heat treatment process is 10-25 mgKOH/g.
According to the technical scheme, the carboxyl-terminated polyester resin prepared by a specific preparation method is selected to be mixed with other raw materials such as epoxy resin and filler, and then the mixture is subjected to stirring, melt extrusion, tabletting, grinding and sieving to prepare the hammer tone powder coating; the whole preparation process is simple and can be used for batch production. In the invention, the carboxyl-terminated polyester resin which is a key component is prepared by the steps of mixing and melting polyol, polyalkyl organic silicon resin and an esterification catalyst, adding aromatic polybasic acid, fatty polybasic acid and the like and raw materials; the carboxyl-terminated polyester resin prepared by the method has excellent weather resistance, so that the prepared hammer powder coating has more excellent heat resistance, aging resistance and stability.
In the above technical solution, the amount and ratio of the raw materials can be selected in a wide range, but in order to improve the heat resistance and stability of the prepared powder coating, the amount ratio of the carboxyl-terminated polyester resin, the epoxy resin, the filler, the hammer agent, the pigment and the low-temperature curing accelerator is preferably 100: 50-70: 20-35: 0.5-1.2: 5-10: 1-5.
In the above technical solution, the working conditions of the extruder can be selected in a wide range, but in order to improve the heat resistance and stability of the prepared powder coating, preferably, the working conditions of the extruder are as follows: the temperature of the first zone of the extruder is 90-100 ℃, and the temperature of the second zone is 105-.
In the above technical solution, the working conditions in the grinding and sieving step can be selected in a wide range, but in order to improve the heat resistance and stability of the prepared hammer powder coating, preferably, the working conditions in the grinding and sieving step are as follows: the main grinding speed of the flour mill is 45-50Hz, the auxiliary grinding speed is 20-35Hz, and the size of the screen is 180-200 meshes.
In the above technical solution, the specific kind of the filler may be selected from a wide range, but in order to improve the heat resistance and stability of the prepared hammer powder coating, preferably, the filler is one or more of carbon black, silica, talc, attapulgite, sodium silicate and sodium alginate.
Also, the specific kinds of the pigment and the low-temperature curing accelerator can be selected within a wide range, but in order to improve the heat resistance and stability of the prepared hammer-grained powder coating, preferably, the pigment is titanium dioxide, the hammer-grained agent is modified cellulose acetate butyrate polymer,
the low-temperature curing accelerator is one or more of 2-phenylimidazoline, 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole and glycoluril.
In the process of preparing the carboxyl-terminated polyester resin, specific amounts of the respective raw materials may be selected within a wide range, but in order to improve the weather resistance of the carboxyl-terminated polyester resin to be produced, it is preferable that the polyalkyl silicone resin is used in an amount of 0.2 to 1 part by weight, the aromatic polybasic acid is used in an amount of 1.5 to 2.5 parts by weight, the aliphatic polybasic acid is used in an amount of 0.04 to 0.2 parts by weight, the acid hydrolysis agent is used in an amount of 0.2 to 0.6 parts by weight, and the esterification catalyst is used in an amount of 0.04 to 0.6 parts by weight, relative to 1 part by weight of the polyol.
In the above-mentioned embodiment, the specific conditions of the heat treatment can be selected within a wide range, but in order to improve the weather resistance of the carboxyl-terminated polyester resin to be produced, it is preferable that the conditions of the heat treatment are: under nitrogen atmosphere, heating to 180-190 ℃ from room temperature at a heating rate of 5-8 ℃/min; then, the temperature is raised to 255 ℃ at a heating rate of 10-15 ℃/min, and the temperature is maintained at 255 ℃ for 8-12 h.
In the above technical scheme, in order to further improve the preparation efficiency and further improve the weather resistance of the carboxyl-terminated polyester resin, preferably, after the acid hydrolysis agent is added, the temperature of the system is kept at 235-255 ℃ for continuously maintaining for 2-4h, and then the system is vacuumized and polycondensed for 4-6 h;
meanwhile, the acid ester range of the system (i.e., the entire reaction system) before the evacuation for the polycondensation may be selected within a wide range, but in order to improve the weather resistance of the high-end carboxyl polyester resin to be produced, it is preferable that the acid value of the system before the evacuation is 36 to 40 mgKOH/g.
Further, after the polycondensation step is completed, the acid value of the system is 30 to 35 mgKOH/g.
In the present invention, the specific kind of the polyalkyl silicone resin may be selected within a wide range, but in order to improve the weather resistance of the resulting high-end carboxyl polyester resin, it is preferable that the polyalkyl silicone resin is polyethyl silicone resin and/or polymethyl silicone resin.
In the above technical solution, the specific molecular weight of the polyethyl silicone resin or polymethylsilicon resin may be selected within a wide range, but in order to improve the weather resistance of the prepared high-end carboxyl polyester resin and to be more suitable for preparing hammer tone powder coating, preferably, the weight average molecular weight of the ethyl silicone resin is 1 to 2 ten thousand, and the weight average molecular weight of the polymethylsilicon resin is 1 to 2 ten thousand.
In the above technical solution, the specific types of the polyol, the aromatic polybasic acid and the aliphatic polybasic acid can be selected within a wide range, but in order to improve the weather resistance of the carboxyl-terminated polyester resin to be obtained, it is preferable that the polyol is one or more of neopentyl glycol, ethylene glycol and 2-methyl-1, 3-propanediol;
the aromatic polybasic acid is terephthalic acid and/or isophthalic acid;
the fatty polybasic acid is adipic acid and/or 1, 4-cyclohexanedicarboxylic acid.
In the above-mentioned technical solution, the specific kinds of the acid hydrolysis agent and the esterification catalyst can be selected within wide ranges, but in order to improve the production efficiency and the weather resistance of the carboxyl-terminated polyester resin produced, it is preferable that the acid hydrolysis agent comprises 1, 4-cyclohexanedicarboxylic acid and/or trimellitic anhydride;
the esterification catalyst is one or more of zinc oxide, montmorillonite, stannous chloride and dibutyl tin dilaurate.
The invention also provides a hammer powder coating prepared by the preparation method.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be described in detail below by way of examples.
Preparation example 1
Mixing neopentyl glycol, polyethylene silicone resin (with the weight-average molecular weight of 1 ten thousand) and stannous chloride, melting, adding terephthalic acid and adipic acid, and heating to 180 ℃ from room temperature at a heating rate of 5 ℃/min under a nitrogen atmosphere; then, the temperature is raised to 235 ℃ at the heating rate of 10 ℃/min, and the temperature is maintained at 235 ℃ for 12h (the acid value of the system in the heat treatment process is 10 mgKOH/g); after the 1, 4-cyclohexanedicarboxylic acid is added, the temperature of the system is kept at 235 ℃ and is continuously maintained for 4 hours (the acid value of the system is 36mgKOH/g), the system is vacuumized and polycondensation is carried out for 4 hours (the acid value of the system is 30 mgKOH/g); finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for the hammer tone powder coating, and recording the carboxyl-terminated polyester resin as W1;
wherein the weight ratio of neopentyl glycol, polyethyl silicone resin, terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and stannous chloride is 1: 0.2: 1.5: 0.04: 0.2: 0.04.
preparation example 2
Mixing and melting 2-methyl-1, 3-propylene glycol, polymethyl silicon resin (weight average molecular weight is 2 ten thousand) and dibutyl tin dilaurate, adding isophthalic acid and 1, 4-cyclohexanedicarboxylic acid, and heating to 185 ℃ from room temperature at a heating rate of 7 ℃/min under nitrogen atmosphere; then, the temperature is raised to 245 ℃ at the temperature raising rate of 12 ℃/min, and the temperature is maintained at 245 ℃ for 10h (the acid value of the system in the heat treatment process is 20 mgKOH/g); after trimellitic anhydride is added, the temperature of the system is kept at 245 ℃ and is continuously maintained for 3 hours (the acid value of the system is 38mgKOH/g), the system is vacuumized and polycondensed for 5 hours (the acid value of the system is 32 mgKOH/g); finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for the hammer tone powder coating; noted as W2;
wherein the weight ratio of 2-methyl-1, 3-propylene glycol, polymethyl silicone resin, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, trimellitic anhydride and dibutyl tin dilaurate is 1: 0.8: 2.0: 0.15: 0.4: 0.3.
preparation example 3
Mixing and melting ethylene glycol, polymethyl silicone resin (with the weight-average molecular weight of 1 ten thousand) and zinc oxide, adding terephthalic acid and adipic acid, and heating to 190 ℃ from the room temperature at the heating rate of 8 ℃/min under nitrogen atmosphere; then, the temperature is raised to 255 ℃ at the temperature rise rate of 15 ℃/min, and the temperature is maintained at 255 ℃ for 8h (the acid value of the system in the heat treatment process is 25 mgKOH/g); after the trimellitic anhydride is added, the system temperature is kept at 255 ℃ and is continuously maintained for 2 hours (the acid value of the system is 40mgKOH/g), the system is vacuumized and polycondensed for 6 hours (the acid value of the system is 35 mgKOH/g); finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for the hammer tone powder coating; denoted as W3.
Wherein the weight ratio of the ethylene glycol, the polymethyl silicone resin, the terephthalic acid, the adipic acid, the trimellitic anhydride and the zinc oxide is 1: 1: 2.5: 0.2: 0.6: 0.6.
preparation example 4
Mixing neopentyl glycol, polyethylene silicone resin (with the weight-average molecular weight of 1 ten thousand) and stannous chloride, melting, adding terephthalic acid and adipic acid, heating to 235 ℃ at a heating rate of 5 ℃/min at room temperature under a nitrogen atmosphere, and maintaining at 235 ℃ for 12h (the acid value of the system is 10mgKOH/g in the heat treatment process); after the 1, 4-cyclohexanedicarboxylic acid is added, the temperature of the system is kept at 235 ℃ and is continuously maintained for 4 hours (the acid value of the system is 36mgKOH/g), the system is vacuumized and polycondensation is carried out for 4 hours (the acid value of the system is 30 mgKOH/g); finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for the hammer tone powder coating, and recording the carboxyl-terminated polyester resin as W4;
wherein the weight ratio of neopentyl glycol, polyethyl silicone resin, terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and stannous chloride is 1: 0.2: 1.5: 0.04: 0.2: 0.04.
preparation example 5
Mixing neopentyl glycol, polyethylene silicone resin (with the weight-average molecular weight of 1 ten thousand) and stannous chloride, melting, adding terephthalic acid and adipic acid, heating to 235 ℃ at the temperature rise rate of 10 ℃/min at room temperature under nitrogen atmosphere, and maintaining at 235 ℃ for 12h (the acid value of the system is 10mgKOH/g in the heat treatment process); after the 1, 4-cyclohexanedicarboxylic acid is added, the temperature of the system is kept at 235 ℃ and is continuously maintained for 4 hours (the acid value of the system is 36mgKOH/g), the system is vacuumized and polycondensation is carried out for 4 hours (the acid value of the system is 30 mgKOH/g); finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for the hammer tone powder coating, and recording the carboxyl-terminated polyester resin as W5;
wherein the weight ratio of neopentyl glycol, polyethyl silicone resin, terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and stannous chloride is 1: 0.2: 1.5: 0.04: 0.2: 0.04.
preparation example 6
A carboxyl-terminated polyester resin for hammer tone powder coating was prepared as in example 1 and designated W6; except that the weight ratio of neopentyl glycol, polyethyl silicone, terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and stannous chloride was 1: 0.15: 1.1: 0.02: 0.1: 0.02.
preparation example 7
A carboxyl-terminated polyester resin for hammer tone powder coating was prepared as in example 1 and designated W7; except that the weight ratio of neopentyl glycol, polyethyl silicone, terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and stannous chloride was 1: 1.2: 2.6: 0.25: 0.7: 0.8.
example 1
Premixing carboxyl-terminated polyester resin W1, epoxy resin, carbon black, silicon dioxide, a hammer agent, pigment and a low-temperature curing accelerator for 6-9min, stirring to obtain a mixture M1, melt-extruding the mixture M1 (the working conditions of an extruder are that the temperature of an area I of the extruder is 90 ℃ and the temperature of an area II of the extruder is 105 ℃), tabletting to obtain sheet materials, grinding and sieving the sheet materials (the working conditions in the grinding and sieving step are that the main grinding rotating speed of a flour mill is 45Hz, the auxiliary grinding rotating speed is 20Hz, and the specification of a screen mesh is 180 meshes) to obtain the hammer powder coating, and recording the mark as A1
Wherein the dosage ratio of the carboxyl-terminated polyester resin W1, the epoxy resin, the carbon black, the silicon dioxide, the modified cellulose acetate butyrate polymer, the titanium pigment and the 2-phenylimidazoline is 100: 50: 10: 10: 0.5: 5: 1.
example 2
Premixing carboxyl-terminated polyester resin W2, epoxy resin, talcum powder, attapulgite, modified cellulose acetate butyrate polymer, titanium dioxide and 2-methylimidazole for 6-9min, stirring to obtain a mixture M1, carrying out melt extrusion on the mixture M1 (the working conditions of an extruder are that the temperature of an area I of the extruder is 95 ℃ and the temperature of an area II of the extruder is 110 ℃), tabletting to obtain a sheet material, and carrying out grinding and sieving on the sheet material (the working conditions in the grinding and sieving step are that the main grinding rotating speed of a flour mill is 50Hz, the auxiliary grinding rotating speed is 30Hz, and the specification of a screen is 200 meshes) to obtain the hammer powder coating, which is marked as A2;
wherein the dosage ratio of the carboxyl-terminated polyester resin W2, the epoxy resin, the talcum powder, the attapulgite, the modified cellulose acetate butyrate polymer, the titanium pigment and the 2-methylimidazole is 100: 60: 15: 15: 1.1: 8: 3.
example 3
Premixing carboxyl-terminated polyester resin W3, epoxy resin, talcum powder, attapulgite, modified cellulose acetate butyrate polymer, titanium dioxide and 2-heptadecyl imidazole for 6-9min, stirring to obtain a mixture M1, melting and extruding the mixture M1 (the working conditions of an extruder are that the temperature of a first area of the extruder is 100 ℃ and the temperature of a second area is 110 ℃), tabletting to obtain a sheet material, and grinding and sieving the sheet material (the working conditions in the grinding and sieving steps are that the main grinding rotating speed of a flour mill is 50Hz, the auxiliary grinding rotating speed is 35Hz, and the specification of a screen is 200 meshes) to obtain the hammer powder coating, which is marked as A3;
wherein the dosage ratio of the carboxyl-terminated polyester resin W3, the epoxy resin, the talcum powder, the attapulgite, the modified cellulose acetate butyrate polymer, the titanium pigment and the 2-heptadecyl imidazole is 100: 50: 15: 15: 0.5: 5: 1.
example 4
A hammer powder coating, designated a4, was prepared according to the method of example 1; except that the carboxyl-terminated polyester resin used was W4.
Example 5
A hammer powder coating, designated a5, was prepared according to the method of example 1; except that the carboxyl-terminated polyester resin used was W5.
Example 6
A hammer powder coating, designated a6, was prepared according to the method of example 1; except that the carboxyl-terminated polyester resin used was W6.
Example 7
A hammer powder coating, designated a7, was prepared according to the method of example 1; except that the carboxyl-terminated polyester resin used was W7.
Detection example 1
The hammer-grained powder coatings obtained in the examples and comparative examples were subjected to an impact resistance test according to the provisions of the national standard GB/T1732 (or ISO 6272):
the prepared powder coating A1-A7 is cured at 120 ℃, 130 ℃ and 140 ℃ for 20min respectively to obtain the hammer powder coating with the coating thickness of 50-80 mu m. Next, a test was conducted using a QCJ impact tester, and the weight adjusted was raised to a height of 50cm from the slide cylinder by using a punch of 1/2. The test piece is horizontally placed on an anvil with the coating film (the thickness of the coating of the powder coating is 50-80 mu m) upward, and the distance between each impacted point of the test piece is not less than 15 mm. And pressing the control button, enabling the heavy hammer to freely fall on the punch, lifting the heavy hammer to take out the test piece, recording the height of the heavy hammer falling on the test piece, and impacting the same test piece at different positions for three times. Observing a test piece subjected to the three-time impact test by using a 4-10 times magnifying lens, and judging whether the coating film has the phenomena of cracking, falling and the like; specific results are shown in table 1.
TABLE 1
According to the detection results in table 1, the curing temperature of the hammer tone powder coating provided by the application can be as low as 120 ℃ to 140 ℃, that is, the hammer tone powder coating can achieve a good curing effect at a low temperature; and the resulting powder coating also has excellent impact resistance.
Detection example 2
The weathering resistance of the hammer powder coatings obtained was tested according to the regulations in GB/T1865 (or ISO 11341): preparing a powder coating with the coating thickness of 50-80 mu m according to the method in the detection example 1, and testing the glossiness of the coating; then respectively recording and calculating the light retention (%) of the powder coating after 480h and 1500h of coating irradiation by a xenon lamp; the specific results are shown in Table 2.
Wherein the gloss retention is (gloss of the coating film after test/gloss of the coating film before test) X100%.
TABLE 2
| 480 h/light retention rate | 1500 h/light-retaining rate% | |
| A1 | 85％ | 65％ |
| A2 | 85％ | 62％ |
| A3 | 83％ | 62％ |
| A4 | 80％ | 55％ |
| A5 | 79％ | 55％ |
| A6 | 55％ | 43％ |
| A7 | 52％ | 40％ |
According to the test results in Table 2, the gloss retention of the hammer tone powder coating A1-A3 provided by the invention is very high, and the gloss retention of the coating irradiated by a xenon lamp after 480 hours is over 80 percent and can reach 85 percent at most; in addition, the light retention rate of the coating can still reach more than 60 percent after the coating is irradiated by a 1500h xenon lamp. In addition, the comparison with the gloss retention of the coating of A4-A7 shows that the preparation method of the invention can obtain higher gloss retention of the powder coating. In addition, after a coating prepared from the A1-A3 powder coating is baked at 300 ℃ for 50min, the coating is good and the gloss retention rate is kept at about 50%, which also shows that the hammer tone powder coating provided by the invention has excellent high temperature resistance and aging resistance.
Detection example 3
The pencil hardness of the powder coatings obtained A1-A7 was tested as specified in the national Standard GB/T6739 (or ISO 15184): the pencil for testing is required to expose 5-6 mm of cylindrical pencil core (the pencil core can not be loosened or damaged by cutting), the end face of the pencil core is smooth, and the edge is sharp (the edge can not be broken or notched). And (3) checking whether the test piece is fixed, wherein the length of the pencil lead and the end face of the pencil are in accordance with the conditions, otherwise, repairing the pencil again by using a pencil sharpener and No. 400 abrasive paper, assembling the pencil, enabling the pencil end to just contact the surface of the coating film, pushing a trolley (750g +/-10 g), enabling the pencil end to contact the coating film, and moving at the speed of about 0.5 mm/s. The test piece and the pencil end are reversely moved by 30mm to scratch. According to the method, five marks are marked on different positions of the surface of the test piece, and the test piece is taken out after marking. According to the steps, starting testing from the hardest 6H pencil, and successively replacing pencils which are lower by one level until pencils which only plough and damage the coating film once in five marks are found out, and taking the hardness of the pencils at the lower level as the hardness of the pencils of the coating film to be tested; at the same time, the hammer clarity of the coating was visually observed. Specific results are shown in Table 3
TABLE 3
| Hardness of pencil | Definition of hammer marks | |
| A1 | 2H | Clear hammer |
| A2 | 3H | Clear hammer |
| A3 | 3H | Clear hammer |
| A4 | ＜2H | Too small hammer |
| A5 | ＜2H | Hammer blur |
| A6 | ＜2H | Hammer blur |
| A7 | ＜2H | Hammer blur |
The preferred embodiments of the present invention have been described in detail with reference to the examples, but the present invention is not limited to the details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A preparation method of hammer-line powder coating is characterized by comprising the following steps:
premixing carboxyl-terminated polyester resin, epoxy resin, a filler, a hammer agent, a pigment and a low-temperature curing accelerator for 6-9min, stirring to obtain a mixture M1, carrying out melt extrusion and tabletting on the mixture M1 to obtain a sheet material, and grinding and sieving the sheet material to obtain the hammer powder coating;
wherein the carboxyl-terminated polyester resin is prepared by the following method:
mixing and melting polyol, polyalkyl organic silicon resin and an esterification catalyst, adding aromatic polybasic acid and fatty polybasic acid, then carrying out heat treatment, and then adding an acidolysis agent for end capping and depolymerization; finally, carrying out vacuum polycondensation to obtain carboxyl-terminated polyester resin for hammer powder coating, wherein the acid value is 10-25mgKOH/g in the heat treatment process;
wherein the dosage ratio of the carboxyl-terminated polyester resin, the epoxy resin, the filler, the hammer agent, the pigment and the low-temperature curing accelerator is 100: 50-70: 20-35: 0.5-1.2: 5-10: 1-5;
wherein, relative to 1 weight part of polyol, the use amount of the polyalkyl organic silicon resin is 0.2 to 1 weight part, the use amount of the aromatic polybasic acid is 1.5 to 2.5 weight parts, the use amount of the fatty polybasic acid is 0.04 to 0.2 weight part, the use amount of the acidolysis agent is 0.2 to 0.6 weight part, and the use amount of the esterification catalyst is 0.0.4 to 0.6 weight part;
the conditions of the heat treatment are as follows: under nitrogen atmosphere, heating to 180-190 ℃ from room temperature at a heating rate of 5-8 ℃/min; then, heating to 235-255 ℃ at a heating rate of 10-15 ℃/min, and maintaining at 235-255 ℃ for 8-12 h;
after the acidolysis agent is added, the temperature of the system is kept at 235-255 ℃ for continuously maintaining for 2-4h, and then the system is vacuumized and polycondensed for 4-6 h; the acid value of the system before vacuumizing is 36-40mgKOH/g,
after the polycondensation step is finished, the acid value of the system is 30-35 mgKOH/g.
2. The production method according to claim 1, wherein the working conditions of the extruder in the melt extrusion step are: the temperature of the first zone of the extruder is 90-100 ℃, and the temperature of the second zone is 105-110 ℃.
3. The manufacturing method according to claim 1, wherein the working conditions in the grinding and sieving step are: the main grinding speed of the flour mill is 45-50Hz, the auxiliary grinding speed is 20-35Hz, and the specification of the screen is 180-200 meshes.
4. The production method according to any one of claims 1 to 3, wherein the filler is one or more of carbon black, silica, talc, attapulgite, sodium silicate and sodium alginate.
5. The production method according to any one of claims 1 to 3, wherein the pigment is titanium dioxide, the hammer tone agent is a modified cellulose acetate butyrate polymer,
the low-temperature curing accelerator is one or more of 2-phenylimidazoline, 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole and glycoluril.
6. The production method according to claim 1, wherein the polyalkyl silicone resin is polyethyl silicone resin and/or polymethyl silicone resin;
the weight average molecular weight of the polyethylene silicone resin is 1-2 ten thousand,
the weight average molecular weight of the polymethyl silicon resin is 1 ten thousand to 2 ten thousand;
the polyalcohol is one or more of neopentyl glycol, ethylene glycol and 2-methyl-1, 3-propylene glycol; the aromatic polybasic acid is terephthalic acid and/or isophthalic acid;
the fatty polybasic acid is adipic acid and/or 1, 4-cyclohexanedicarboxylic acid;
the acidolysis agent comprises 1, 4-cyclohexanedicarboxylic acid and/or trimellitic anhydride;
the esterification catalyst is one or more of zinc oxide, montmorillonite, stannous chloride and dibutyl tin dilaurate.
7. A hammer powder coating obtained by the production method according to any one of claims 1 to 6.
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Denomination of invention: Hammer grain powder coating and its preparation method Effective date of registration: 20210924 Granted publication date: 20201027 Pledgee: China Construction Bank Corporation Fanchang sub branch Pledgor: ANHUI MEIJIA NEW MATERIAL Co.,Ltd. Registration number: Y2021980009733 |
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