CN112063295B - Low-gloss bending-resistant powder coating and preparation method thereof - Google Patents

Low-gloss bending-resistant powder coating and preparation method thereof Download PDF

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CN112063295B
CN112063295B CN202010921243.4A CN202010921243A CN112063295B CN 112063295 B CN112063295 B CN 112063295B CN 202010921243 A CN202010921243 A CN 202010921243A CN 112063295 B CN112063295 B CN 112063295B
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李红
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Ningbo Aiyong New Material Technology Co ltd
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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
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/06—Polysulfones; Polyethersulfones
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention provides a low-gloss bending-resistant powder coating and a preparation method thereof. Wherein the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid as raw materials. The coating film formed by the powder coating has the advantages of low gloss, good bending resistance, good impact resistance and the like.

Description

Low-gloss bending-resistant powder coating and preparation method thereof
Technical Field
The invention relates to the technical field of coating processing, in particular to a low-gloss bending-resistant powder coating and a preparation method thereof.
Background
The powder coating is a green coating produced by a non-volatile organic solvent, has a completely different form from general coatings, exists in a state of fine powder, and is rapidly developed in various countries in the world due to the characteristics of resource saving, no solvent, low pollution, high efficiency, one-step coating forming, wide application field and the like.
The prior noble and luxurious decorative high-gloss coating is favored by consumers due to the advantages of bright and bright color and luster and the like; but at the same time, the high-glossiness coating film has serious light reflection, which causes eye fatigue; while low gloss surfaces provide a quiet, natural feel, are not obtrusive, and are not prone to user fatigue, low gloss appearance is becoming more and more popular, and the demand for low gloss coatings with a soft appearance is increasing dramatically. Furthermore, in certain special coating fields, such as aluminum profiles, automobile parts, metal furniture, hardware, lamps and other industrial fields, the use of extremely low-gloss powder coatings is required.
The degree of gloss depends on the smoothness of the surface of the object, so that paint matting is actually achieved by increasing the microroughness of the surface of the paint film by controlling the different components or parts of the polymer to be cured at different speeds so that the paint film shrinks differently, thereby forming an irregular surface structure.
Powder coatings are typically matted using the following route:
1. physical extinction method: delustering caused by adding delustering fillers (such as delustering calcium, delustering barium, wollastonite, kaolin, clay and the like) or materials incompatible with a system and the like; the physical extinction has the advantages of low cost and simplicity; the disadvantages are that the extinction degree is limited, and is generally about 30 degrees at the lowest; the gloss was not stable enough and the reproducibility was poor (greatly affected by extrusion conditions, curing conditions, etc.).
2. And (3) extinction wax: the extinction degree is limited, and the powder coating with low gloss is difficult to prepare, and the degree is generally higher than 30 ℃; secondly, the wax cannot be used in large quantity, and the wax can migrate to the surface of a coating film to cause fogging and repainting performance obstacles; thirdly, the baking will smoke; powder is easy to agglomerate.
3. Chemical extinction method: by chemical reaction, usually a plurality of reactive substances are introduced into the system, and the difference in curing reaction rate is utilized to cause uneven shrinkage of the cured coating film, thereby resulting in microscopic unevenness and dullness of the coating film surface. The chemical extinction has the advantages of low gloss, stable general gloss and good reproducibility. However, the compatibility between different resins is not always good, and the mechanical performance indexes such as bending resistance and impact resistance of the product are affected.
Patent application CN107641451A discloses a matte powder coating, which is prepared from raw materials such as saturated carboxyl-terminated polyester resin, high hydroxyl-terminated polyester resin, low hydroxyl-terminated polyester resin, etc., and by blending different types of resins, a wider gloss range is achieved, but the lowest gloss is only 20 degrees, and the low gloss requirement in a special field cannot be met.
Disclosure of Invention
The invention aims to provide a low-gloss bending-resistant powder coating and a preparation method thereof, wherein the low-gloss bending-resistant powder coating has low gloss, excellent mechanical properties and good bending resistance and impact resistance.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a low-gloss bending-resistant powder coating comprises the following specific steps:
(1) firstly, polyester resin and polyether sulfone resin are mixed according to the mass ratio of 1: 5-6, mixing and extruding to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 5-6 hours at 28-30 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain the low-gloss bending-resistant powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
Preferably, in step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 2-3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the temperature of the first section is 130-150 ℃, the temperature of the second section is 325-335 ℃, the temperature of the third section is 350-370 ℃, and the temperature of the fourth section is 290-310 ℃.
Preferably, in step (1), the polyethersulfone resin is A-304P, Suwei, USA.
Preferably, in the step (1), the acid value of the polyester resin is 35-38 mgKOH/g, the glass transition temperature is 47-49 ℃, the average branching degree is 2-2.2, and the average molecular weight is 3000-6000; the polyester resin is prepared from the following components in parts by weight: 30-35 parts of 2-methyl-2, 4-pentanediol, 0.1-0.8 part of trimethylolpropane, 50-60 parts of terephthalic acid, 4-10 parts of acidolysis agent, 0.1-0.2 part of catalyst and 0.1-0.2 part of antioxidant.
More preferably, the acidolysis agent is one or a mixture of isophthalic acid and adipic acid; the catalyst is monobutyl tin oxide; the antioxidant is one or a mixture of more of triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrapropionate.
Further preferably, the preparation method of the polyester resin is as follows: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120-130 ℃, adding terephthalic acid, uniformly stirring, heating to 160-170 ℃, starting reaction, heating to 230-240 ℃ at the speed of 10-15 ℃/h, preserving heat at the temperature until a reaction system is clear, reducing the temperature of the reaction system to 200-210 ℃, adding an acidolysis agent, heating to 220-230 ℃, preserving heat for 2 hours, reacting for 2-4 hours under the condition that the vacuum degree is-0.09 to-0.099 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30-40 minutes, and discharging.
Preferably, in the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 5-8 mL.
Preferably, in the step (2), the preparation method of the sphingomonas bacterium liquid is as follows: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107～108cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 2-3% of trehalose, 1-1.5% of white carbon black, 4-5% of sodium pyruvate, 2003-5% of polyethylene glycol and the balance of water.
Preferably, in the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 2-3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150-180 ℃, the second-stage temperature is 320-340 ℃, the third-stage temperature is 360-380 ℃, and the fourth-stage temperature is 300-320 ℃.
Preferably, in the step (3), the grinding time of the sand mill is 3-6 hours.
Preferably, in the step (3), the mass ratio of the modified resin, the curing agent, the filler and the leveling agent is 10: 0.9-1.1: 0.6-0.8: 0.02-0.03.
Preferably, in the step (3), the curing agent is a phenol novolac resin or dicyandiamide; the flatting agent is selected from one or more of polydimethylsiloxane, polymethylphenylsiloxane, acrylic resin, urea-formaldehyde resin and melamine-formaldehyde resin.
Preferably, in step (3), the filler is prepared by the following method: under a nitrogen atmosphere, mixing butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane according to a molar ratio of 1-2: 1-2: 4-8 are respectively dissolved in n-hexane to form solutions with respective mass concentrations of 10-12%, then the solution of butyl dichloroborane and the solution of methyl dichlorosilane are simultaneously dropped into the solution of hexamethyldisilazane, and heating, stirring and reacting are carried out to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
The low-gloss bending-resistant powder coating is obtained by the preparation method.
The invention has the beneficial effects that:
the invention uses polyester resin and polyether sulfone resin as main raw materials to prepare composite resin, then the composite resin is fermented and modified by sphingosine monad to obtain modified resin, and finally the modified resin is mixed and extruded with a curing agent, a filler and a flatting agent, and the mixture is ground by a sand mill to obtain the low-gloss bending-resistant powder coating. Wherein the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid as raw materials. The coating film formed by the powder coating has the advantages of low gloss, good bending resistance, good impact resistance and the like.
The polyester resin is prepared by taking 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid as raw materials, wherein benzene rings are introduced into the terephthalic acid as the raw material; the polyether sulfone resin is used as another resin raw material, wherein the polyether sulfone resin also contains benzene rings, and the polyether sulfone resin and the benzene rings are compounded to have good compatibility, so that mechanical performance indexes such as bending resistance, impact resistance and the like cannot be influenced. Most importantly, the composite resin formed by compounding the two is fermented and modified by sphingomonas, and the sphingomonas is fermented to degrade benzene rings, so that the unevenness of a microstructure is promoted, a rough surface is formed, the diffuse reflection degree of light is increased, and the glossiness is reduced.
The filler is prepared by taking butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane as raw materials, and the component of the filler is polyborosilazane, wherein imino contained in the polyborosilazane and sulfonyl of polyether sulfone resin form hydrogen bonds, so that the compatibility is enhanced, the mechanical enhancement effect is realized, and the bending resistance and the impact resistance of the product are further improved; on the other hand, surface branching is also advantageous in increasing the surface roughness and further reducing the glossiness.
Detailed Description
The technical solutions in the embodiments of the present invention will be 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 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 sphingomonas according to the present invention, ATCC31461, was purchased from Shanghai valley research industries, Ltd.
Example 1
A preparation method of a low-gloss bending-resistant powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 5kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 5 hours at 30 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain the low-gloss bending-resistant powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 130 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 350 ℃, and the fourth-stage temperature is 310 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 35mgKOH/g, the glass transition temperature is 49 ℃, the average branching degree is 2, and the average molecular weight is 6000; the polyester resin is prepared from the following components: 30kg of 2-methyl-2, 4-pentanediol, 0.8kg of trimethylolpropane, 50kg of terephthalic acid, 10kg of acidolysis agent, 0.1kg of catalyst and 0.2kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is triphenyl phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120 ℃, adding terephthalic acid, uniformly stirring, heating to 170 ℃ for starting reaction, then heating to 240 ℃ at the speed of 10 ℃/h, preserving heat at the temperature until a reaction system is clear, then reducing the temperature of the reaction system to 200 ℃, adding an acidolysis agent, then heating to 230 ℃, preserving heat for 2 hours, reacting for 4 hours under the condition that the vacuum degree is-0.09 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 8 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 3% of trehalose, 1% of white carbon black, 5% of sodium pyruvate, 2003% of polyethylene glycol and the balance of water.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 340 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 320 ℃.
In the step (3), the grinding time of the sand mill is 3 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 1.1: 0.6: 0.03.
In the step (3), the curing agent is linear phenolic resin; the leveling agent is polydimethylsiloxane.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1: 2: 4, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentration of 12%, then simultaneously dripping the solution of butyl dichloroborane and the solution of methyl dichlorosilane into the solution of hexamethyldisilazane, and heating, stirring and reacting to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Example 2
A preparation method of a low-gloss bending-resistant powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 6kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 6 hours at 28 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain the low-gloss bending-resistant powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 2 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 325 ℃, the third-stage temperature is 370 ℃, and the fourth-stage temperature is 290 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 38mgKOH/g, the glass transition temperature is 47 ℃, the average branching degree is 2.2, and the average molecular weight is 3000; the polyester resin is prepared from the following components: 35kg of 2-methyl-2, 4-pentanediol, 0.1kg of trimethylolpropane, 60kg of terephthalic acid, 4kg of acidolysis agent, 0.2kg of catalyst and 0.1kg of antioxidant.
The acidolysis agent is adipic acid; the catalyst is monobutyl tin oxide; the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 130 ℃, adding terephthalic acid, uniformly stirring, heating to 160 ℃, starting reaction, heating to 230 ℃ at the speed of 15 ℃/h, preserving heat at the temperature until a reaction system is clear, reducing the temperature of the reaction system to 210 ℃, adding an acidolysis agent, heating to 220 ℃, preserving heat for 2 hours, reacting for 2 hours under the condition that the vacuum degree is-0.099 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 40 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingosine monad bacterial liquid is 1 mg: 5 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 108cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 2% of trehalose, 1.5% of white carbon black, 4% of sodium pyruvate, 2005% of polyethylene glycol and the balance of water.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 2 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 180 ℃, the second-stage temperature is 320 ℃, the third-stage temperature is 380 ℃, and the fourth-stage temperature is 300 ℃.
In the step (3), the grinding time of the sand mill is 6 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 0.9: 0.8: 0.02.
in the step (3), the curing agent is dicyandiamide; the leveling agent is acrylic resin.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 2: 1: 8, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 10%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating and stirring the solution to react to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Example 3
A preparation method of a low-gloss bending-resistant powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 5.5kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 5.5 hours at 29 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain the low-gloss bending-resistant powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 2.5 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 140 ℃, the second-stage temperature is 330 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 300 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 36mgKOH/g, the glass transition temperature is 48 ℃, the average branching degree is 2.1, and the average molecular weight is 4000; the polyester resin is prepared from the following components: 32kg of 2-methyl-2, 4-pentanediol, 0.5kg of trimethylolpropane, 55kg of terephthalic acid, 8kg of acidolysis agent, 0.15kg of catalyst and 0.15kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is pentaerythritol tetrapropionate.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 125 ℃, adding terephthalic acid, uniformly stirring, heating to 165 ℃ for starting reaction, then heating to 235 ℃ at the speed of 12 ℃/h, preserving heat at the temperature until a reaction system is clear, then reducing the temperature of the reaction system to 205 ℃, adding an acidolysis agent, then heating to 225 ℃, preserving heat for 2 hours, reacting for 3 hours under the condition that the vacuum degree is-0.095 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 35 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 6 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strains, adding the activated Sphingomonas strains into a buffer solution, and adjusting the concentration of the activated Sphingomonas strains to be 108cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: trehalose 2.5%, white carbon black 1.3%, sodium pyruvate 4.5%, polyethylene glycol 2004%, and the balance water.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 2.5 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 170 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 375 ℃, and the fourth-stage temperature is 310 ℃.
In the step (3), the grinding time of the sand mill is 4 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 1: 0.7: 0.025.
in the step (3), the curing agent is linear phenolic resin; the leveling agent is melamine formaldehyde resin.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1.5: 1.5: 6, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 11%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating and stirring the solution to react to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Comparative example 1
A preparation method of powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 4kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 5 hours at 30 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain a powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 130 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 350 ℃, and the fourth-stage temperature is 310 ℃.
In the step (1), the polyether sulfone resin is A-304P, Suwei in America.
In the step (1), the acid value of the polyester resin is 35mgKOH/g, the glass transition temperature is 49 ℃, the average branching degree is 2, and the average molecular weight is 6000; the polyester resin is prepared from the following components: 30kg of 2-methyl-2, 4-pentanediol, 0.8kg of trimethylolpropane, 50kg of terephthalic acid, 10kg of acidolysis agent, 0.1kg of catalyst and 0.2kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is triphenyl phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120 ℃, adding terephthalic acid, uniformly stirring, heating to 170 ℃ for starting reaction, then heating to 240 ℃ at the speed of 10 ℃/h, preserving heat at the temperature until a reaction system is clear, then reducing the temperature of the reaction system to 200 ℃, adding an acidolysis agent, then heating to 230 ℃, preserving heat for 2 hours, reacting for 4 hours under the condition that the vacuum degree is-0.09 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 8 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weightThe preparation method comprises the following steps: trehalose 3%, white carbon black 1%, sodium pyruvate 5%, polyethylene glycol 2003%, and the balance of water.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 340 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 320 ℃.
In the step (3), the grinding time of the sand mill is 3 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 1.1: 0.6: 0.03.
In the step (3), the curing agent is linear phenolic resin; the leveling agent is polydimethylsiloxane.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1: 2: 4, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 12%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating, stirring and reacting to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Comparative example 2
A preparation method of powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 5kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 7 hours at 30 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain a powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 130 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 350 ℃, and the fourth-stage temperature is 310 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 35mgKOH/g, the glass transition temperature is 49 ℃, the average branching degree is 2, and the average molecular weight is 6000; the polyester resin is prepared from the following components: 30kg of 2-methyl-2, 4-pentanediol, 0.8kg of trimethylolpropane, 50kg of terephthalic acid, 10kg of acidolysis agent, 0.1kg of catalyst and 0.2kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is triphenyl phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120 ℃, adding terephthalic acid, uniformly stirring, heating to 170 ℃ for starting reaction, then heating to 240 ℃ at the speed of 10 ℃/h, preserving heat at the temperature until a reaction system is clear, then reducing the temperature of the reaction system to 200 ℃, adding an acidolysis agent, then heating to 230 ℃, preserving heat for 2 hours, reacting for 4 hours under the condition that the vacuum degree is-0.09 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 8 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 3% of trehalose, 1% of white carbon black, 5% of sodium pyruvate, 2003% of polyethylene glycol and the balance of water.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 340 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 320 ℃.
In the step (3), the grinding time of the sand mill is 3 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 1.1: 0.6: 0.03.
In the step (3), the curing agent is linear phenolic resin; the leveling agent is polydimethylsiloxane.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1: 2: 4, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 12%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating, stirring and reacting to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Comparative example 3
A preparation method of powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 5kg of polyether sulfone resin to obtain composite resin;
(2) then mixing and extruding the composite resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain a powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and terephthalic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 130 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 350 ℃, and the fourth-stage temperature is 310 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 35mgKOH/g, the glass transition temperature is 49 ℃, the average branching degree is 2, and the average molecular weight is 6000; the polyester resin is prepared from the following components: 30kg of 2-methyl-2, 4-pentanediol, 0.8kg of trimethylolpropane, 50kg of terephthalic acid, 10kg of acidolysis agent, 0.1kg of catalyst and 0.2kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is triphenyl phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120 ℃, adding terephthalic acid, uniformly stirring, heating to 170 ℃ for starting reaction, then heating to 240 ℃ at the speed of 10 ℃/h, preserving heat at the temperature until a reaction system is clear, then reducing the temperature of the reaction system to 200 ℃, adding an acidolysis agent, then heating to 230 ℃, preserving heat for 2 hours, reacting for 4 hours under the condition that the vacuum degree is-0.09 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30 minutes, and discharging.
In the step (2), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 340 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 320 ℃.
In the step (2), the grinding time of the sand mill is 3 hours.
In the step (2), the mass ratio of the composite resin, the curing agent, the filler and the flatting agent is 10: 1.1: 0.6: 0.03.
In the step (2), the curing agent is linear phenolic resin; the leveling agent is polydimethylsiloxane.
In the step (2), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1: 2: 4, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 12%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating, stirring and reacting to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Comparative example 4
A preparation method of powder coating comprises the following specific steps:
(1) firstly, mixing and extruding 1kg of polyester resin and 5kg of polyether sulfone resin to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain a powder coating;
the polyester resin is prepared from 2-methyl-2, 4-pentanediol, trimethylolpropane and adipic acid serving as raw materials.
In the step (1), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 130 ℃, the second-stage temperature is 335 ℃, the third-stage temperature is 350 ℃, and the fourth-stage temperature is 310 ℃.
In the step (1), the polyether sulfone resin is A-304P, American Suwei.
In the step (1), the acid value of the polyester resin is 35mgKOH/g, the glass transition temperature is 49 ℃, the average branching degree is 2, and the average molecular weight is 6000; the polyester resin is prepared from the following components: 30kg of 2-methyl-2, 4-pentanediol, 0.8kg of trimethylolpropane, 50kg of adipic acid, 10kg of acidolysis agent, 0.1kg of catalyst and 0.2kg of antioxidant.
The acidolysis agent is isophthalic acid; the catalyst is monobutyl tin oxide; the antioxidant is triphenyl phosphite.
The preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120 ℃, adding adipic acid, uniformly stirring, heating to 170 ℃ for starting reaction, heating to 240 ℃ at the speed of 10 ℃/h, preserving heat at the temperature until a reaction system is clear, reducing the temperature of the reaction system to 200 ℃, adding an acidolysis agent, heating to 230 ℃, preserving heat for 2 hours, reacting for 4 hours under the condition that the vacuum degree is-0.09 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30 minutes, and discharging.
In the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 8 mL.
In the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 3% of trehalose, 1% of white carbon black, 5% of sodium pyruvate, 2003% of polyethylene glycol and the balance of water.
In the step (2), the fermentation modification process conditions are as follows: fermenting and modifying for 5 hours at 30 ℃.
In the step (3), the specific method of mixing and extruding is as follows: firstly, mixing for 3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the first-stage temperature is 150 ℃, the second-stage temperature is 340 ℃, the third-stage temperature is 360 ℃, and the fourth-stage temperature is 320 ℃.
In the step (3), the grinding time of the sand mill is 3 hours.
In the step (3), the mass ratio of the modified resin, the curing agent, the filler and the flatting agent is 10: 1.1: 0.6: 0.03.
In the step (3), the curing agent is linear phenolic resin; the leveling agent is polydimethylsiloxane.
In the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane are mixed according to a molar ratio of 1: 2: 4, respectively dissolving the raw materials in n-hexane to form solutions with respective mass concentrations of 12%, then simultaneously dripping the solution of butyl dichloroborane and methyl dichlorosilane into the solution of hexamethyldisilazane, and heating, stirring and reacting to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
Test examples
The powder coatings obtained in examples 1 to 3 and comparative examples 1 to 4 were spray-cured (aluminum alloy hub surface, coating thickness 80 μm), and after curing, the coating was subjected to a performance test comprising:
directly detecting the glossiness by using an intelligent glossiness meter (Shanghai Rongjida instrument science and technology limited);
impact resistance: GB/T1732-1993;
bending resistance: GB/T6742-1986;
cupping test: GB/T9753-2007.
The results are shown in Table 1.
TABLE 1 Performance test results
Glossiness (degree) Impact Strength (kg. cm) Bending resistance (cylindrical axis, mm) Cupping test (mm)
Example 1 5 62 ≤1 8
Example 2 4 63 ≤1 8
Example 3 3 65 ≤1 9
Comparative example 1 5 58 2 6
Comparative example 2 5 56 3 6
Comparative example 3 30 60 1 7
Comparative example 4 10 57 2 7
As shown in Table 1, the coating films obtained from the powder coatings of examples 1 to 3 have low gloss, high impact strength, good bending resistance, high cupping value and good mechanical properties.
Comparative example 1 in step (1), the mass ratio of the polyester resin to the polyethersulfone resin is 1:4, and the use amount of the polyethersulfone resin is reduced, so that the mechanical properties of the product are directly influenced; comparative example 2 in the step (2), the fermentation modification time is 7 hours, and the fermentation time is prolonged, so that benzene rings are excessively degraded, and the mechanical properties of the product are influenced; comparative example 3 step (2) was omitted, no modification of the roughness by fermentation modification, and gloss was directly affected; comparative example 4 in the preparation of polyester resin, adipic acid was used instead of terephthalic acid, and no benzene ring was introduced, affecting the mechanical properties and gloss of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (7)

1. The preparation method of the low-gloss bending-resistant powder coating is characterized by comprising the following specific steps of:
(1) firstly, polyester resin and polyether sulfone resin are mixed according to the mass ratio of 1: 5-6, mixing and extruding to obtain composite resin;
(2) then soaking the composite resin in sphingosine monad bacterial liquid, fermenting and modifying for 5-6 hours at 28-30 ℃, and centrifuging to obtain modified resin;
(3) finally, mixing and extruding the modified resin, a curing agent, a filler and a flatting agent, and grinding by a sand mill to obtain the low-gloss bending-resistant powder coating;
the polyester resin is prepared from the following components in parts by weight: 30-35 parts of 2-methyl-2, 4-pentanediol, 0.1-0.8 part of trimethylolpropane, 50-60 parts of terephthalic acid, 4-10 parts of acidolysis agent, 0.1-0.2 part of catalyst and 0.1-0.2 part of antioxidant;
wherein in the step (1), the acid value of the polyester resin is 35-38 mgKOH/g, the glass transition temperature is 47-49 ℃, the average branching degree is 2-2.2, and the average molecular weight is 3000-6000;
wherein the acidolysis agent is one or a mixture of isophthalic acid and adipic acid; the catalyst is monobutyl tin oxide; the antioxidant is one or a mixture of more of triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrapropionate;
the preparation method of the polyester resin comprises the following steps: adding 2-methyl-2, 4-pentanediol, trimethylolpropane and a catalyst into a reactor in a nitrogen atmosphere, heating to 120-130 ℃, adding terephthalic acid, uniformly stirring, heating to 160-170 ℃, starting reaction, heating to 230-240 ℃ at the speed of 10-15 ℃/h, preserving heat at the temperature until a reaction system is clear, reducing the temperature of the reaction system to 200-210 ℃, adding an acidolysis agent, heating to 220-230 ℃, preserving heat for 2 hours, reacting for 2-4 hours under the condition that the vacuum degree is-0.09-0.099 Mpa, adding an antioxidant after the acid value index is qualified, stirring for 30-40 minutes, and discharging;
wherein, in the step (2), the preparation method of the sphingomonas bacterium liquid comprises the following steps: activating Sphingomonas strain, adding into buffer solution, and adjusting the concentration of the bacteria to 107～108cfu/mL; the buffer solution is prepared by mixing the following components in percentage by weight: 2-3% of trehalose, 1-1.5% of white carbon black, 4-5% of sodium pyruvate, 2003-5% of polyethylene glycol and the balance of water;
wherein, in the step (3), the filler is prepared by the following method: under a nitrogen atmosphere, mixing butyl dichloroborane, methyl dichlorosilane and hexamethyldisilazane according to a molar ratio of 1-2: 1-2: 4-8 are respectively dissolved in n-hexane to form solutions with respective mass concentrations of 10-12%, then the solution of butyl dichloroborane and the solution of methyl dichlorosilane are simultaneously dropped into the solution of hexamethyldisilazane, and heating, stirring and reacting are carried out to obtain a precursor; and finally, carrying out heat treatment on the precursor in an ammonia atmosphere, and naturally cooling to room temperature (25 ℃) to obtain the filler.
2. The method according to claim 1, wherein in the step (1), the mixing and extruding are carried out by the following specific method: firstly, mixing for 2-3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the temperature of the first section is 130-150 ℃, the temperature of the second section is 325-335 ℃, the temperature of the third section is 350-370 ℃, and the temperature of the fourth section is 290-310 ℃.
3. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the polyester resin to the polyethersulfone resin is 1: 5 to 6.
4. The method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the composite resin to the sphingomonas bacterium liquid is 1 mg: 5-8 mL.
5. The preparation method according to claim 1, wherein in the step (3), the mixing and extruding are carried out by the following specific method: firstly, mixing for 2-3 minutes by using a mixer, and then extruding by using an extruder, wherein the specific working conditions are as follows: the temperature of the first section is 150-180 ℃, the temperature of the second section is 320-340 ℃, the temperature of the third section is 360-380 ℃, and the temperature of the fourth section is 300-320 ℃.
6. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the modified resin, the curing agent, the filler and the leveling agent is 10: 0.9-1.1: 0.6-0.8: 0.02-0.03.
7. A low gloss bend resistant powder coating obtainable by the process of any one of claims 1 to 6.
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