CN115160892B - Low-temperature curing powder coating and preparation method thereof - Google Patents

Low-temperature curing powder coating and preparation method thereof Download PDF

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CN115160892B
CN115160892B CN202210926996.3A CN202210926996A CN115160892B CN 115160892 B CN115160892 B CN 115160892B CN 202210926996 A CN202210926996 A CN 202210926996A CN 115160892 B CN115160892 B CN 115160892B
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张东杰
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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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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Abstract

The invention discloses a low-temperature curing powder coating and a preparation method thereof, wherein the low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 8-15 parts of allylamino triazinyl glycinamide oxyphenyl film-forming polymer, 25-35 parts of hyperbranched epoxy resin, 5-10 parts of low-temperature curing agent, 20-30 parts of inorganic filler, 10-20 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of leveling agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode. The low-temperature cured powder coating disclosed by the invention has the advantages of good performance stability, strong adhesion with a base material, good aging resistance, excellent moist heat resistance and solvent resistance and low curing temperature.

Description

Low-temperature curing powder coating and preparation method thereof
Technical Field
The invention relates to the technical field of powder coatings, in particular to a low-temperature curing powder coating and a preparation method thereof.
Background
In recent years, along with the development of economy, the progress of society and the improvement of living standard of people, more and more people begin to pursue high-quality life, and as a common decoration material, paint is often covered on the surface of a coating object to form a coating film, so that visual aesthetic feeling is improved, the coating object is protected from being corroded by external environment, and the use safety and environmental protection directly influence the living grade and quality of people. Therefore, development of a coating material excellent in safety in use and environmental protection is a hot subject of the industrial study.
As a common safe and environment-friendly coating, the powder coating is widely applied to rust prevention treatment of building decoration and outdoor metal parts due to the characteristics of no solvent, no pollution, energy and resource saving, labor intensity reduction, high mechanical strength of coating film and the like, is a main stream direction of development of the coating industry in the current or even future period, and has great potential value. However, conventional powder coatings generally require a long curing time at 180-200 ℃ to cure into a film, and the high requirements of curing conditions are disadvantageous for energy conservation, and the powder coatings cannot be applied to high-temperature sensitive substrates, severely limiting the application range of the powder coatings. Therefore, how to effectively reduce the curing temperature and curing time of powder coatings has been a concern in the powder coating industry.
The existing low-temperature curing powder coating has the defects of more or less poor mechanical stability and chemical stability, insufficient ageing resistance, poor adhesion with a base material and short service life, and is disclosed in Chinese patent document CN 103160195B. The composite material is prepared from the following raw materials in parts by weight: 250-300 parts of epoxy resin (E-12), 350-400 parts of polyester resin (P6060), 3-5 parts of flatting agent (PV 88), 3-5 parts of brightening agent (BLC 701B), 4-6 parts of benzoin, 5-10 parts of 2-phenylimidazoline, 4-6 parts of 2-methylimidazole, 50-80 parts of high-gloss barium sulfate, 40-60 parts of quasi-spherical silicon micropowder, 5-8 parts of solid paraffin and 280-320 parts of organic coated titanium dioxide. The powder coating prepared by the invention has the advantages of high hardness, high strength, good heat resistance, good ageing resistance, quick curing time, environmental protection, no pollution and the like. The coating film has excellent performance, high performance indexes in various aspects of acid and alkali resistance, salt fog resistance, gasoline resistance and other organic solvents, and particularly has plump paint film and outstanding luster. However, the curing temperature is still higher, the comprehensive performance and performance stability of the coating film are still required to be further improved, and the weather resistance is required to be further improved.
Therefore, the low-temperature curing powder coating with good performance stability, strong adhesive force with a base material, good ageing resistance, excellent moist heat resistance and solvent resistance and low curing temperature and the preparation method thereof are developed, meet the market demand, have wide market value and application prospect, and have very important significance for promoting the further development of the powder coating.
Disclosure of Invention
The invention mainly aims to provide the low-temperature curing powder coating with good performance stability, strong adhesive force with a base material, good ageing resistance, excellent moist heat resistance and solvent resistance and low curing temperature and the preparation method thereof.
In order to achieve the above purpose, the invention provides a low-temperature curing powder coating, which is characterized by being prepared from the following raw materials in parts by weight: 8-15 parts of allylamino triazinyl glycinamide oxyphenyl film-forming polymer, 25-35 parts of hyperbranched epoxy resin, 5-10 parts of low-temperature curing agent, 20-30 parts of inorganic filler, 10-20 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of leveling agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 2246.
Preferably, the leveling agent is at least one of a BYK-333 leveling agent and an HY-5030 leveling agent of the Pick BYK.
Preferably, the photoinitiator is at least one of benzoin and benzoin diethyl ether.
Preferably, the coupling agent is a silane coupling agent KH560.
Preferably, the preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 60-70 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
Preferably, the mass ratio of the glycidyl methacrylate, the methyl vinyl silafluorene, the N-acryloylmorpholine, the 1-isopropenyl-2-benzimidazolone, the initiator and the high boiling point solvent is 1 (0.7-1): (0.3-0.6): (0.8-1.2): (0.03-0.05): (15-25).
Preferably, the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the inorganic filler is at least one of double fly powder, talcum powder and titanium dioxide; the granularity of the inorganic filler is 1200-1800 meshes.
Preferably, the hyperbranched epoxy resin is hyperbranched epoxy resin HyPer E102, which is purchased from the chemical Co., ltd.
Preferably, the preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 3-6 hours at the temperature of 30-40 ℃, and removing the solvent by rotary evaporation to obtain the allylamino triazinyl glycidoxyphenyl film-forming polymer.
Preferably, the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, 2-bis- (4-glycidoxy-l) propane and the organic solvent is 1:1 (6-10).
Preferably, the organic solvent is any one of ethanol, isopropanol and acetone.
Another object of the present invention is to provide a method for preparing the low temperature curing powder coating, comprising the steps of: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 150-200 mesh sieve to obtain the low-temperature cured powder coating.
Preferably, the mixing temperature is 75-85 ℃.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The low-temperature curing powder coating disclosed by the invention can be realized by adopting conventional processes and equipment, has the advantages of low investment, low energy consumption, convenience in operation, high preparation efficiency and high finished product qualification rate, and is suitable for continuous industrial production.
(2) The low-temperature curing powder coating disclosed by the invention adopts allylamino triazinyl glycidoxyphenyl film-forming polymer, hyperbranched epoxy resin and glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer as film-forming substances, has good film-forming effect, and has the advantages of good film-forming effect, cooperation effect, simultaneous introduction of triazinyl, glycidoxyphenyl, hyperbranched epoxy resin base, silafluorenyl, morpholinyl and benzimidazolone in a film molecular structure, cooperation among the three, and excellent moisture-proof and solvent-proof properties under multiple effects such as electronic effect, steric effect and conjugate effect, and the like, so that the prepared coating has good performance stability, strong adhesive force with a base material, good ageing resistance and excellent moisture-proof and solvent resistance.
(3) The low-temperature curing powder coating disclosed by the invention adopts a low-temperature curing agent to be matched with a film forming substance, so that the curing temperature of the prepared powder coating is low, an allyl amino triazinyl glycinamide oxyphenyl film forming polymer containing ethylenic bonds can undergo a copolymerization crosslinking reaction under the action of a photoinitiator, and in the mixing process, a glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer can also undergo a grafting reaction with a component containing unsaturated ethylenic bonds; meanwhile, the component containing epoxy groups can react with a low-temperature curing agent, so that the coating film forms an interpenetrating network structure, and the performance stability, ageing resistance, hardness, moist heat resistance and solvent resistance of the coating film are effectively improved.
(4) The low-temperature curing powder coating disclosed by the invention takes air as a dispersion medium, the environmental protection performance is better, the allyl amino triazinyl glycinamine oxyphenyl film-forming polymer containing olefinic bonds is prepared by epoxy ring-opening reaction, hydroxyl is introduced in the epoxy ring-opening reaction process, and the adhesive force between the coating and a substrate can be improved.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
The hyperbranched epoxy resin in the embodiment of the invention is hyperbranched epoxy resin HyPer E102, which is purchased from the chemical Co-Ltd.
Example 1
A low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 8 parts of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 25 parts of hyperbranched epoxy resin, 5 parts of low-temperature curing agent, 20 parts of inorganic filler, 10 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5 part of coupling agent, 1 part of photoinitiator, 0.5 part of flatting agent and 0.2 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
The antioxidant is antioxidant 1010; the leveling agent is a German Pick BYK leveling agent BYK-333; the photoinitiator is benzoin; the coupling agent is silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 3 hours at 60 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 3 times, and finally drying the polymer in a vacuum drying oven at 85 ℃ to constant weight to obtain a glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer; the glycidyl methacrylate, methyl vinyl silicon fluorene, N-acryloylmorpholine and 1-isopropenyl-2-benzimidazolone, initiator, high boiling point solvent in a mass ratio of 1:0.7:0.3:0.8:0.03:15; the initiator is azodiisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; m of the copolymer by GPC test n =7336g/mol，M W /M n =1.275; the quantitative analysis of EDX element proves that the mass ratio of structural units respectively introduced by glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine and 1-isopropenyl-2-benzimidazolone in the copolymer is 0.99:0.68:0.3:0.79.
The inorganic filler is double fly powder; the granularity of the inorganic filler is 1200 meshes.
The preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 3 hours at 30 ℃, and removing the solvent by rotary evaporation to obtain an allylamino triazinyl glycidoxyphenyl film-forming polymer; the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the 2, 2-bis- (4-glycidoxy-benzene) propane to the organic solvent is 1:1:6; the organic solvent is ethanol; m of the Polymer by GPC test n =2336g/mol，M W /M n =1.264；
The preparation method of the low-temperature curing powder coating comprises the following steps: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 150-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature was 75 ℃.
Example 2
A low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 10 parts of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 27 parts of hyperbranched epoxy resin, 6 parts of low-temperature curing agent, 23 parts of inorganic filler, 12 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.7 part of coupling agent, 1.5 parts of photoinitiator, 0.7 part of leveling agent and 0.3 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
The antioxidant is antioxidant 168; the leveling agent is an organosilicon leveling agent HY-5030; the photoinitiator is benzoin diethyl ether; the coupling agent is silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 3.5 hours at 62 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and finally drying the polymer in a vacuum drying oven at 87 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methyl vinyl silafluorene to the N-acryloylmorpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high boiling point solvent is 1:0.8:0.4:0.9:0.035:17; the initiator is azodiisobutyronitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The inorganic filler is talcum powder; the granularity of the inorganic filler is 1300 meshes.
The preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 4 hours at 33 ℃, and removing the solvent by rotary evaporation to obtain an allylamino triazinyl glycidoxyphenyl film-forming polymer; the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the 2, 2-bis- (4-glycidoxy-benzene) propane to the organic solvent is 1:1:7; the organic solvent is isopropanol.
The preparation method of the low-temperature curing powder coating comprises the following steps: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 160-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature was 78 ℃.
Example 3
A low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 13 parts of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 30 parts of hyperbranched epoxy resin, 7.5 parts of low-temperature curing agent, 25 parts of inorganic filler, 15 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 1 part of coupling agent, 2 parts of photoinitiator, 1 part of flatting agent and 0.35 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
The antioxidant is antioxidant 2246; the leveling agent is a German Pick BYK leveling agent BYK-333; the photoinitiator is benzoin diethyl ether; the coupling agent is silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 4 hours at 65 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying the polymer in a vacuum drying oven at 90 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methyl vinyl silafluorene to the N-acryloylmorpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high boiling point solvent is 1:0.85:0.45:1:0.04:20; the initiator is azodiisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The inorganic filler is titanium dioxide; the granularity of the inorganic filler is 1500 meshes.
The preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 4.5 hours at 35 ℃, and then removing the solvent by rotary evaporation to obtain an allylamino triazinyl glycidoxyphenyl film-forming polymer; the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the 2, 2-bis- (4-glycidoxy-benzene) propane to the organic solvent is 1:1:8; the organic solvent is acetone.
The preparation method of the low-temperature curing powder coating comprises the following steps: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 180-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature was 80 ℃.
Example 4
The low-temperature curing powder coating is characterized by being prepared from the following raw materials in parts by weight: 14 parts of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 33 parts of hyperbranched epoxy resin, 9 parts of low-temperature curing agent, 28 parts of inorganic filler, 18 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 1.3 parts of coupling agent, 2.5 parts of photoinitiator, 1.3 parts of flatting agent and 0.45 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
The antioxidant is a mixture formed by mixing an antioxidant 1010, an antioxidant 168 and an antioxidant 2246 according to a mass ratio of 1:2:2; the leveling agent is a mixture formed by mixing a BYK-333 leveling agent of Pick BYK and an HY-5030 leveling agent of organic silicon according to a mass ratio of 3:5; the photoinitiator is a mixture formed by mixing benzoin and benzoin diethyl ether according to a mass ratio of 1:3; the coupling agent is silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 4.5 hours at 68 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying the polymer in a vacuum drying oven at 93 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methyl vinyl silafluorene to the N-acryloylmorpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high boiling point solvent is 1:0.95:0.55:1.1:0.045:23; the initiator is azodiisobutyronitrile; the high boiling point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide according to a mass ratio of 1:2:1; the inert gas is argon.
The inorganic filler is a mixture formed by mixing double fly powder, talcum powder and titanium dioxide according to the mass ratio of 1:1:1; the granularity of the inorganic filler is 1700 meshes.
The preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 5.5 hours at 38 ℃, and then removing the solvent by rotary evaporation to obtain an allylamino triazinyl glycidoxyphenyl film-forming polymer; the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the 2, 2-bis- (4-glycidoxy-benzene) propane to the organic solvent is 1:1:9.5; the organic solvent is ethanol.
The preparation method of the low-temperature curing powder coating comprises the following steps: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 190-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature was 83 ℃.
Example 5
A low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 15 parts of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 35 parts of hyperbranched epoxy resin, 10 parts of low-temperature curing agent, 30 parts of inorganic filler, 20 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 1.5 parts of coupling agent, 3 parts of photoinitiator, 1.5 parts of flatting agent and 0.5 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
The antioxidant is antioxidant 1010; the leveling agent is a German Pick BYK leveling agent BYK-333; the photoinitiator is benzoin diethyl ether; the coupling agent is silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 5 hours at 70 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying the polymer in a vacuum drying oven at 95 ℃ to constant weight to obtain a glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer; the mass ratio of the glycidyl methacrylate to the methyl vinyl silafluorene to the N-acryloylmorpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high boiling point solvent is 1:1:0.6:1.2:0.05:25; the initiator is azodiisobutyronitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is nitrogen.
The inorganic filler is double fly powder; the granularity of the inorganic filler is 1800 meshes.
The preparation method of the allylamino triazinyl glycinamide oxyphenyl film-forming polymer comprises the following steps: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 6 hours at 40 ℃, and removing the solvent by rotary evaporation to obtain an allylamino triazinyl glycidoxyphenyl film-forming polymer; the molar ratio of the 2, 4-diamino-6-diallylamino-1, 3, 5-triazine to the 2, 2-bis- (4-glycidoxy-benzene) propane to the organic solvent is 1:1:10; the organic solvent is isopropanol.
The preparation method of the low-temperature curing powder coating comprises the following steps: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 200-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature was 85 ℃.
Comparative example 1
The invention provides a low temperature curing powder coating, the formula and preparation method of which are similar to those of example 1, except that allylamino triazinyl glycinamide oxyphenyl film forming polymer is not added.
Comparative example 2
The invention provides a low-temperature curing powder coating, which has a formula and a preparation method similar to those of an example 1, except that 1-isopropenyl-2-benzimidazolone and N-acryloylmorpholine are not added in the preparation process of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
The low temperature cured powder coating samples prepared in examples 1-5 and comparative examples 1-2 above were subjected to the relevant performance tests, the test results and test methods are shown in Table 1. The curing conditions of each coating are as follows: curing at 110 ℃ for 8min; the 3KW ultraviolet mercury lamp was irradiated for 30 seconds.
TABLE 1
Project Solvent rub resistance Surface moisture and heat resistance Anti-artificial aging for 1000h Salt spray resistance test 1200h Adhesion force
Test standard GB/T 23989-2009 GB/T 4893.2-2005 GB/T 1865-2009 GB/T 1771-2007 GB/T 9286-1998
Example 1 By passing through Level 1 By passing through By passing through Level 1
Example 2 By passing through Level 1 By passing through By passing through Level 1
Example 3 By passing through Level 1 By passing through By passing through Level 1
Example 4 By passing through Level 1 By passing through By passing through Level 1
Example 5 By passing through Level 1 By passing through By passing through Level 1
Comparative example 1 Not pass through Level 2 Not pass through Not pass through 3 grade
Comparative example 2 Not pass through Level 2 Not pass through Not pass through Level 2
As can be seen from table 1, the low-temperature cured powder coating disclosed by the embodiment of the invention has excellent solvent resistance, damp and heat resistance, artificial aging resistance and salt spray resistance, and has better adhesive force; the addition of allylamino triazinyl glycinamide oxyphenyl film forming polymer, 1-isopropenyl-2-benzimidazolone and N-acryloylmorpholine is beneficial for improving the above properties.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The low-temperature curing powder coating is characterized by being prepared from the following raw materials in parts by weight: 8-15 parts of allylamino triazinyl glycinamide oxyphenyl film-forming polymer, 25-35 parts of hyperbranched epoxy resin, 5-10 parts of low-temperature curing agent, 20-30 parts of inorganic filler, 10-20 parts of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of leveling agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinamide oxyphenyl film-forming polymer is prepared from 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycinamide oxyphenyl) propane through an epoxy ring-opening reaction in an end-to-end connection mode.
2. The low temperature curable powder coating of claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 2246; the leveling agent is at least one of a BYK-333 leveling agent and an HY-5030 leveling agent of the Pick BYK.
3. The low temperature curable powder coating of claim 1, wherein the photoinitiator is at least one of benzoin, benzoin diethyl ether; the coupling agent is silane coupling agent KH560.
4. The low temperature curing powder coating as claimed in claim 1, wherein the preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone and an initiator into a high boiling point solvent, stirring and reacting for 3-5 hours at 60-70 ℃ in an inert gas atmosphere, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer.
5. The low-temperature-curable powder coating according to claim 4, wherein the mass ratio of glycidyl methacrylate, methyl vinyl silafluorene, N-acryloylmorpholine, 1-isopropenyl-2-benzimidazolone, initiator and high boiling point solvent is 1 (0.7-1): (0.3-0.6): (0.8-1.2): (0.03-0.05): (15-25).
6. The low temperature cure powder coating according to claim 4, wherein the initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the inert gas is any one of nitrogen, helium, neon and argon.
7. The low temperature curable powder coating of claim 1, wherein the inorganic filler is at least one of fine powder, talc, titanium pigment; the granularity of the inorganic filler is 1200-1800 meshes; the hyperbranched epoxy resin is hyperbranched epoxy resin HyPer E102.
8. The low temperature cure powder coating of claim 1, wherein the method of preparing the allylamino triazinyl glycinamide oxyphenyl film forming polymer comprises the steps of: adding 2, 4-diamino-6-diallylamino-1, 3, 5-triazine and 2, 2-bis- (4-glycidoxyphenyl) propane into an organic solvent, stirring and reacting for 3-6 hours at the temperature of 30-40 ℃, and removing the solvent by rotary evaporation to obtain the allylamino triazinyl glycidoxyphenyl film-forming polymer.
9. The low temperature curable powder coating of claim 8, wherein the molar ratio of 2, 4-diamino-6-diallylamino-1, 3, 5-triazine, 2-bis- (4-glycidoxy-l) propane, organic solvent is 1:1 (6-10); the organic solvent is any one of ethanol, isopropanol and acetone.
10. A method for preparing a low temperature curable powder coating according to any one of claims 1 to 9, comprising the steps of: mixing the raw materials according to the weight parts uniformly, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the obtained particles by an ACM jet mill, and sieving the crushed particles by a 150-200-mesh sieve to obtain the low-temperature cured powder coating; the mixing temperature is 75-85 ℃.
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Publication number Priority date Publication date Assignee Title
CN111349189A (en) * 2020-04-26 2020-06-30 杨光云 Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof
CN114316492A (en) * 2022-01-19 2022-04-12 慈溪埃弗龙密封件有限公司 Long-life toothed plate reinforced high-strength graphite gasket and preparation method thereof
CN114801402A (en) * 2022-02-14 2022-07-29 宁波东方席业有限公司 Weather-proof, moisture-proof and fireproof multifunctional mat and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111349189A (en) * 2020-04-26 2020-06-30 杨光云 Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof
CN114316492A (en) * 2022-01-19 2022-04-12 慈溪埃弗龙密封件有限公司 Long-life toothed plate reinforced high-strength graphite gasket and preparation method thereof
CN114801402A (en) * 2022-02-14 2022-07-29 宁波东方席业有限公司 Weather-proof, moisture-proof and fireproof multifunctional mat and preparation method thereof

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