CN115160892A - Low-temperature curing powder coating and preparation method thereof - Google Patents
Low-temperature curing powder coating and preparation method thereof Download PDFInfo
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- CN115160892A CN115160892A CN202210926996.3A CN202210926996A CN115160892A CN 115160892 A CN115160892 A CN 115160892A CN 202210926996 A CN202210926996 A CN 202210926996A CN 115160892 A CN115160892 A CN 115160892A
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- 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
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- 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
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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 glycinyl 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-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of flatting agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxyphenyl) propane through an end-to-end epoxy ring-opening reaction. The low-temperature curing powder coating disclosed by the invention has the advantages of good performance stability, strong adhesion with a base material, good aging resistance, excellent humidity resistance and solvent resistance and low curing temperature.
Description
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, 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, the coating is often coated on the surface of a coating to form a coating film, so that the visual aesthetic feeling is improved, the coating is protected from the erosion of the external environment, and the use safety and the environmental protection directly influence the living quality and the quality of people. Therefore, the development of a coating with excellent safety and environmental protection is a hot topic of research in the industry.
As a common safe and environment-friendly coating, the powder coating is widely applied to building decoration and rust prevention treatment of outdoor metal parts due to the characteristics of no solvent, no pollution, energy and resource saving, labor intensity reduction, high mechanical strength of a coating film and the like, is a mainstream direction for the development of the coating industry at present and even in a period of time in future and has very great potential value. However, the conventional powder coating usually needs a temperature of 180-200 ℃ for curing for a long time to form a film, the high requirement of curing conditions is not favorable for energy conservation, and the powder coating cannot be applied to high-temperature sensitive substrates, thereby severely limiting the application range of the powder coating. Therefore, how to effectively reduce the curing temperature and the curing time of the powder coating is always a concern in the powder coating industry.
The existing low-temperature curing powder coating has the defects of poor mechanical stability and chemical stability, insufficient aging resistance, poor adhesion with a base material and short service life, for example, a low-temperature curing type epoxy/polyester powder coating is disclosed in Chinese patent document CN 103160195B. The feed 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 brightener (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 silica 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 aging resistance, quick curing time, environmental protection, no pollution and the like. The coating film has excellent performance, and has high performance indexes in all aspects of acid and alkali resistance, salt mist resistance, gasoline resistance and other organic solvents, and particularly has plump paint film and outstanding luster. However, the curing temperature is still high, the overall performance and performance stability of the coating film are still to be further improved, and the weather resistance is still to be further improved.
Therefore, the development of the low-temperature curing powder coating which has good performance stability, strong adhesion with a base material, good aging resistance, excellent humidity resistance and solvent resistance and low curing temperature and the preparation method thereof meet market requirements, 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 a low-temperature curing powder coating which has the advantages of good performance stability, strong adhesion with a base material, good aging resistance, excellent humidity and heat resistance and solvent resistance and low curing temperature, and a preparation method thereof.
In order to achieve the aim, 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 glycinyl 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-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of flatting agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
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 German Bick BYK leveling agent BYK-333 and an organic silicon leveling agent HY-5030.
Preferably, the photoinitiator is at least one of benzoin and benzoin ethyl ether.
Preferably, the coupling agent is a silane coupling agent KH560.
Preferably, the preparation method of the glycidyl methacrylate/methylvinylsilfluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the copolymer of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone.
Preferably, the mass ratio of the glycidyl methacrylate to the methylvinyl silafluorene to the N-acryloyl morpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to 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 heavy calcium carbonate, talcum powder and titanium dioxide; the particle size of the inorganic filler is 1200-1800 meshes.
Preferably, the hyperbranched epoxy resin is hyperbranched epoxy resin HyPer E102, available from Wuhan hyperbranched resin technology, inc.
Preferably, the preparation method of the allylamino triazinyl glycinyloxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane into an organic solvent, stirring and reacting for 3-6 hours at 30-40 ℃, and then removing the solvent by rotary evaporation to obtain the allylamino triazinyl glycinyloxyphenyl film-forming polymer.
Preferably, the molar ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane and organic solvent is 1:1 (6-10).
Preferably, the organic solvent is any one of ethanol, isopropanol and acetone.
The invention also aims to provide a preparation method of the low-temperature curing powder coating, which comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the particles by using an ACM jet mill, and sieving the particles by using a 150-200-mesh sieve to obtain the low-temperature curing 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, is low in capital investment, low in energy consumption, convenient to operate, high in preparation efficiency and finished product qualification rate, and suitable for continuous industrial production.
(2) The invention discloses a low-temperature curing powder coating, which adopts allylamino triazinyl glycinyl oxyphenyl film-forming polymer, hyperbranched epoxy resin and glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer to be compounded as film-forming substances, has good film-forming effect, and the combination of the film-forming substances and the hyperbranched epoxy resin, the silafluorene, the morpholine and the benzimidazolone is simultaneously introduced into the molecular structure of a coating film and mutually matched, so that the prepared coating has good performance stability, strong adhesion with a base material, good aging resistance, and excellent moisture and heat resistance and solvent resistance under the multiple actions of electronic effect, steric effect, conjugated effect and the like.
(3) The invention discloses a low-temperature curing powder coating, which 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 allylamino triazinyl glycinyl oxyphenyl film-forming polymer containing ethylenic bonds can generate copolymerization crosslinking reaction under the action of a photoinitiator, and in the mixing process, a glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer can also generate grafting reaction with a component containing unsaturated ethylenic bonds; meanwhile, the component containing epoxy group can react with the low-temperature curing agent chemically, so that the coating film forms an interpenetrating network structure, and the performance stability, aging resistance, hardness, humidity 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, has better environmental protection performance, is prepared from an allylamino triazinyl glycinyl oxyphenyl film-forming polymer containing an ethylenic bond through an epoxy ring-opening reaction, can introduce hydroxyl in the epoxy ring-opening reaction process, and can improve the adhesive force between a coating and a base material.
Detailed Description
The following description is provided to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The hyperbranched epoxy resin provided by the embodiment of the invention is hyperbranched epoxy resin HyPer E102 which is purchased from Wuhan hyperbranched resin technology, inc.
Example 1
The low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 8 parts of allylamino triazinyl glycinyl 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-acryloyl morpholine/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 glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
The antioxidant is 1010; the flatting agent is a German PyK flatting agent BYK-333; the photoinitiator is benzoin; the coupling agent is a silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain a copolymer of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone; the mass ratio of the glycidyl methacrylate to the methylvinyl silafluorene to the N-acryloyl morpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high-boiling point solvent is 1.7; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen; m of the copolymer by GPC measurement n =7336g/mol，M W /M n =1.275; the mass ratio of the structural units respectively introduced by glycidyl methacrylate, methylvinylsilfluorene, N-acryloylmorpholine and 1-isopropenyl-2-benzimidazolone in the copolymer, which is confirmed by EDX elemental quantitative analysis, is 0.99.
The inorganic filler is double-flying powder; the particle size of the inorganic filler is 1200 meshes.
The preparation method of the allylamino triazinyl glycinyl oxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycyloxybenzene) propane into an organic solvent, stirring for reaction at 30 ℃ for 3 hours, and then performing rotary evaporation to remove the solvent to obtain the allylamino triazinyl glycyloxyphenyl film-forming polymer; the molar ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane, organic solvent is 1; the above-mentionedThe organic solvent is ethanol; m of the polymer by GPC measurement n =2336g/mol，M W /M n =1.264；
A preparation method of the low-temperature curing powder coating comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the crushed particles by using an ACM jet mill, and sieving the crushed particles by using a 150-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature was 75 ℃.
Example 2
The low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 10 parts of allylamino triazinyl glycinyl 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-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.7 part of coupling agent, 1.5 parts of photoinitiator, 0.7 part of flatting agent and 0.3 part of antioxidant; the allylamino triazinyl glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
The antioxidant is antioxidant 168; the leveling agent is an organic silicon leveling agent HY-5030; the photoinitiator is benzoin ethyl ether; the coupling agent is a silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 87 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methylvinyl silafluorene to the N-acryloyl morpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high-boiling point solvent is 1.8; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The inorganic filler is talcum powder; the particle size of the inorganic filler is 1300 meshes.
The preparation method of the allylamino triazinyl glycinyl oxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane into an organic solvent, stirring and reacting for 4 hours at 33 ℃, and then performing rotary evaporation to remove the solvent to obtain the allylamino triazinyl glycinyloxyphenyl film-forming polymer; 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane, organic solvent in a molar ratio of 1; the organic solvent is isopropanol.
A preparation method of the low-temperature curing powder coating comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the particles by using an ACM jet mill, and sieving the particles by using a 160-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature was 78 ℃.
Example 3
The low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 13 parts of allylamino triazinyl glycinyl 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-acryloyl morpholine/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 glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
The antioxidant is an antioxidant 2246; the flatting agent is a German PyK flatting agent BYK-333; the photoinitiator is benzoin ethyl ether; the coupling agent is a silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methylvinyl silafluorene to the N-acryloyl morpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high-boiling point solvent is 1.85; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The inorganic filler is titanium dioxide; the particle size of the inorganic filler is 1500 meshes.
The preparation method of the allylamino triazinyl glycinyl oxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) 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 glycinyloxyphenyl film-forming polymer; the molar ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane, organic solvent is 1; the organic solvent is acetone.
A preparation method of the low-temperature curing powder coating comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the particles by using an ACM jet mill, and sieving the particles by using a 180-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature is 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 glycinyl 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-acryloyl morpholine/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 glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
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; the leveling agent is a mixture formed by mixing a German Bick BYK leveling agent BYK-333 and an organic silicon leveling agent HY-5030 according to the mass ratio of 3:5; the photoinitiator is a mixture formed by mixing benzoin and benzoin ethyl ether according to the mass ratio of 1:3; the coupling agent is a silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 93 ℃ to constant weight to obtain the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer.
The mass ratio of the glycidyl methacrylate to the methylvinyl silafluorene to the N-acryloyl morpholine to the 1-isopropenyl-2-benzimidazolone to the initiator to the high-boiling point solvent is 1.95 to 0.55; the initiator is azobisisobutyronitrile; 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; the inert gas is argon.
The inorganic filler is a mixture formed by mixing double flying powder, talcum powder and titanium dioxide according to a mass ratio of 1; the particle size of the inorganic filler is 1700 meshes.
The preparation method of the allylamino triazinyl glycinyl oxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycyloxybenzene) propane into an organic solvent, stirring and reacting for 5.5 hours at 38 ℃, and then performing rotary evaporation to remove the solvent to obtain the allylamino triazinyl glycyloxyphenyl film-forming polymer; the molar ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane, organic solvent is 1; the organic solvent is ethanol.
A preparation method of the low-temperature curing powder coating comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the crushed particles by using an ACM jet mill, and sieving the crushed particles by using a 190-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature was 83 ℃.
Example 5
The low-temperature curing powder coating is prepared from the following raw materials in parts by weight: 15 parts of allylamino triazinyl glycinyl 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-acryloyl morpholine/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 glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxyphenyl) propane through an end-to-end epoxy ring-opening reaction.
The antioxidant is 1010; the flatting agent is a German BYK flatting agent BYK-333; the photoinitiator is benzoin ethyl ether; the coupling agent is a silane coupling agent KH560.
The preparation method of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 95 ℃ to constant weight to obtain a glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer; the mass ratio of the glycidyl methacrylate, the methylvinyl silafluorene, the N-acryloyl morpholine, the 1-isopropenyl-2-benzimidazolone, the initiator and the high-boiling point solvent is (1) and (1.2); the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylformamide; the inert gas is nitrogen.
The inorganic filler is double flying powder; the particle size of the inorganic filler is 1800 meshes.
The preparation method of the allylamino triazinyl glycinyl oxyphenyl film-forming polymer comprises the following steps: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane into an organic solvent, stirring and reacting for 6 hours at 40 ℃, and then performing rotary evaporation to remove the solvent to obtain the allylamino triazinyl glycinyloxyphenyl film-forming polymer; the molar ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) propane, organic solvent is 1; the organic solvent is isopropanol.
A preparation method of the low-temperature curing powder coating comprises the following steps: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the crushed particles by using an ACM jet mill, and sieving the crushed particles by using a 200-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature was 85 ℃.
Comparative example 1
The invention provides a low temperature curing powder coating, the formulation and preparation method of which are similar to those of example 1, except that no allylamino triazinyl glycinyloxyphenyl film-forming polymer is added.
Comparative example 2
The invention provides a low-temperature curing powder coating, the formula and the preparation method are similar to those of the embodiment 1, except that 1-isopropenyl-2-benzimidazolone and N-acryloyl morpholine are not added in the preparation process of the glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer.
The low temperature curing powder coating samples prepared in examples 1-5 and comparative examples 1-2 above were subjected to the relevant performance tests, and the test results and test methods are shown in table 1. The curing conditions of the coatings in each case are as follows: curing at 110 deg.C for 8min; a 3KW ultraviolet mercury lamp was irradiated for 30 seconds.
TABLE 1
| Item | Solvent resistance wiping | Surface moisture and heat resistance | Resisting 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 | Level 1 | By passing | By passing | Level 1 |
| Example 2 | By passing | Level 1 | By passing | By passing | Level 1 |
| Example 3 | By passing | Level 1 | By passing | By passing | Level 1 |
| Example 4 | By passing | Level 1 | By passing | By passing | Level 1 |
| Example 5 | By passing | Level 1 | By passing | By passing | Level 1 |
| Comparative example 1 | Do not pass through | Stage 2 | Do not pass through | Do not pass through | Grade 3 |
| Comparative example 2 | Do not pass through | Stage 2 | Do not pass through | Do not pass through | Stage 2 |
As can be seen from Table 1, the low-temperature curing powder coating disclosed by the embodiment of the invention has excellent solvent resistance, heat and humidity resistance, artificial aging resistance and salt spray resistance, and better adhesion; the addition of an allylaminotriazinylglycinyloxyphenyl film-forming polymer, 1-isopropenyl-2-benzimidazolone and N-acryloylmorpholine are all beneficial in improving these properties.
The foregoing shows and describes the general principles, essential 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, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. 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 glycinyl 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-acryloyl morpholine/1-isopropenyl-2-benzimidazolone copolymer, 0.5-1.5 parts of coupling agent, 1-3 parts of photoinitiator, 0.5-1.5 parts of flatting agent and 0.2-0.5 part of antioxidant; the allylamino triazinyl glycinyloxyphenyl film-forming polymer is prepared from 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane through an end-to-end epoxy ring-opening reaction.
2. The low-temperature curing powder coating as claimed in claim 1, wherein the antioxidant is at least one of an antioxidant 1010, an antioxidant 168 and an antioxidant 2246; the leveling agent is at least one of a German Bick BYK leveling agent BYK-333 and an organic silicon leveling agent HY-5030.
3. The low-temperature curing powder coating as claimed in claim 1, wherein the photoinitiator is at least one of benzoin and benzoin ethyl ether; the coupling agent is a silane coupling agent KH560.
4. The low-temperature curing powder coating as claimed in claim 1, wherein the preparation method of the glycidyl methacrylate/methylvinylsilfluorene/N-acryloylmorpholine/1-isopropenyl-2-benzimidazolone copolymer comprises the following steps: adding glycidyl methacrylate, methyl vinyl silafluorene, N-acryloyl morpholine, 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, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain the copolymer of glycidyl methacrylate/methyl vinyl silafluorene/N-acryloyl morpholine/1-isopropenyl-2-benzimidazolone.
5. The low-temperature-curable powder coating according to claim 4, wherein the mass ratio of the glycidyl methacrylate, the methylvinylsilfluorene, the N-acryloylmorpholine, the 1-isopropenyl-2-benzimidazolone, the initiator and the high-boiling solvent is 1 (0.7-1): 0.3-0.6): 0.8-1.2): 0.03-0.05): 15-25.
6. The low temperature-curable 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. Low-temperature-curing powder coating according to claim 1, the inorganic filler is at least one of double-flying powder, talcum powder and titanium dioxide; the particle size of the inorganic filler is 1200-1800 meshes; the hyperbranched epoxy resin is hyperbranched epoxy resin HyPer E102.
8. A low temperature curing powder coating as claimed in claim 1, wherein the process for the preparation of the allylaminotriazinylglycinyloxyphenyl film forming polymer comprises the steps of: adding 2,4-diamino-6-diallylamino-1,3,5-triazine and 2,2-bis- (4-glycinyloxybenzene) propane into an organic solvent, stirring and reacting for 3-6 hours at 30-40 ℃, and then removing the solvent by rotary evaporation to obtain the allylamino triazinyl glycinyloxyphenyl film-forming polymer.
9. The low temperature curing powder coating of claim 8, wherein the mole ratio of 2,4-diamino-6-diallylamino-1,3,5-triazine, 2,2-bis- (4-glycidoxybenzene) 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 curing powder coating according to any one of claims 1-9, comprising the steps of: uniformly mixing the raw materials in parts by weight, adding the mixture into an extruder for mixing, extruding and granulating, coarsely crushing the obtained particles, crushing the crushed particles by using an ACM jet mill, and sieving the crushed particles by using a 150-200-mesh sieve to obtain a low-temperature curing powder coating; the mixing temperature is 75-85 ℃.
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| 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 |
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