CN119875442B - Fluorocarbon powder coating and preparation method thereof - Google Patents
Fluorocarbon powder coating and preparation method thereof Download PDFInfo
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- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
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Abstract
本发明公开了一种氟碳粉末涂料及其制备方法，属于粉末涂料技术领域，包括以下步骤：将甲基丙烯酸甲酯、甲基丙烯酸羟乙酯、甲基丙烯酸六氟丁酯和对香豆酸甲酯进行预混，得到预混液；将预混液转移至反应釜，升温，加引发剂，进行反应，过滤，干燥，得到改性丙烯酸树脂，进行熔融混炼，挤出，得到物料A；将PVDF氟碳树脂和填料放入反应釜中，升温，搅拌，得到物料B，加入物料A、改性PMMA，搅拌，冷却压片，得到粉末涂料。本发明氟碳粉末涂料，能够保持高耐候性优势的同时，还能够提升内部的相容性和抗紫外性能，并提高双层粉体内部粘结效果。The invention discloses a fluorocarbon powder coating and a preparation method thereof, which belongs to the technical field of powder coatings, and comprises the following steps: premixing methyl methacrylate, hydroxyethyl methacrylate, hexafluorobutyl methacrylate and methyl p-coumarate to obtain a premixed liquid; transferring the premixed liquid to a reactor, heating, adding an initiator, reacting, filtering, drying, obtaining a modified acrylic resin, melt-mixing, extruding, and obtaining material A; placing PVDF fluorocarbon resin and filler into a reactor, heating, stirring, obtaining material B, adding material A and modified PMMA, stirring, cooling and tableting, and obtaining a powder coating. The fluorocarbon powder coating of the invention can maintain the advantages of high weather resistance, while also improving the internal compatibility and UV resistance, and improving the internal bonding effect of the double-layer powder.
Description
Technical Field
The invention relates to the technical field of powder coatings, in particular to a fluorocarbon powder coating and a preparation method thereof.
Background
The fluorocarbon paint is a new type of coating material, which is modified and processed based on fluorocarbon resin and features that the resin contains great amount of F-C bonds with bond energy 485kJmol -1 and high bond energy, so that it has very long weather resistance and chemical corrosion resistance. With global climate change, the demand for building and traffic facilities against extreme climate conditions is continuously increasing, and the super-weather-resistant fluorocarbon coating also has good market adaptability.
Although fluorocarbon resins have high weatherability, such as PVDF (polyvinylidene fluoride) fluorocarbon resins, they have low adhesion and poor compatibility, resulting in affecting the overall mechanical properties. In order to solve the problem, the prior art mainly introduces functional groups with high reactivity into a molecular chain by modifying PVDF, such as a grafting method, and introduces one or more grafting monomers into the PVDF molecular chain, so that although the adhesive force of the modified PVDF fluorocarbon resin powder coating is improved, the high stability, oxidation resistance and weather resistance of the PVDF fluorocarbon resin are obviously reduced, and the reaction is complex and difficult.
In addition, the adhesive force of the coating can be improved by adding the acrylic resin for blending, but the ultraviolet resistance of the acrylic resin is low, the weather resistance is poor, the overall weather resistance is influenced by adding the acrylic resin, and the ultraviolet resistance and the weather resistance are influenced. In order to improve the ultraviolet resistance of the acrylic resin, a metal oxide is generally added as a filler, but the addition of the metal oxide easily affects the overall compatibility effect. Therefore, how to make the added acrylic resin not affect the weather resistance, and keep good compatibility and promote the anti-ultraviolet performance as much as possible is a great problem at present.
In addition, with the global high concern for environmental protection, various places are in charge of related policies to promote the use of low-VOC and environmental-friendly products, so that powder coatings are generated. The powder type paint has no solvent, is more environment-friendly, and is more convenient and faster in storage, transportation and use, and cost is saved, but the compatibility of the paint is also more difficult to grasp, and phase separation and the like are easy to occur, in particular to PVDF fluorocarbon powder paint. The existing double-layer powder technology can improve the adhesive force and weather resistance of the paint, but no suitable bonding auxiliary agent exists, so that the bonding effect between layers is poor, the time is long, and the problems of partial layer separation, bubbles or cracking and the like can also occur.
Disclosure of Invention
In view of the above, the invention provides a fluorocarbon powder coating and a preparation method thereof, which can improve the internal compatibility and ultraviolet resistance and improve the internal bonding effect of double-layer powder while maintaining the advantage of high weather resistance.
In order to achieve the above purpose, the invention provides a preparation method of fluorocarbon powder coating, comprising the following steps:
s1, premixing methyl methacrylate, hydroxyethyl methacrylate, hexafluorobutyl methacrylate, methyl p-coumarate and a solvent to obtain a premix;
s2, transferring the premix to a reaction kettle, heating, adding an initiator, reacting, filtering and drying to obtain modified acrylic resin;
s3, uniformly mixing the modified acrylic resin and the filler, and carrying out melt mixing and extrusion to obtain a material A;
s4, placing PVDF fluorocarbon resin and filler into a reaction kettle, heating, stirring to obtain a material B, adding the material A and modified PMMA, uniformly mixing, cooling and tabletting to obtain the powder coating;
The modified PMMA is obtained by modifying PMMA by adopting 2, 3-pentafluoropropyl acrylate;
the mass ratio of the material A to the material B is (2-3) to (7-8);
in the premix, the mass ratio of hexafluorobutyl methacrylate is 3-8%.
By adopting the technical scheme, the obtained modified acrylic resin can not only improve the ultraviolet resistance of the modified acrylic resin, improve the weather resistance, but also improve the adhesiveness of fluorocarbon powder coating, and by adopting a double-layer powder technology, a film formed after coating is more prone to gathering a large number of hydrophobic fluorocarbon resin layers (materials B) with larger surface tension on the surface layer, and more modified acrylic resin layers (materials A) with smaller relative surface tension and larger adhesiveness are gathered on the bottom, and the modified PMMA is adopted as a bonding auxiliary agent, so that the compatibility of the materials A and B can be improved while the bonding effect is achieved, and the occurrence of layer separation phenomenon is better avoided.
By modifying the acrylic resin with the methyl coumarate, the methyl coumarate has good oxidation resistance, can form phenol free radicals with stable resonance, absorbs a part of energy in ultraviolet rays, can capture and neutralize the free radicals when the ultraviolet radiation generates some free radicals, further improves the ultraviolet resistance of the acrylic resin, has high matching degree between double bonds and ester groups contained in the methyl coumarate and an acrylic monomer, can be subjected to free radical copolymerization to form an irregular copolymer, and can not bring compatibility and other problems while improving the ultraviolet resistance. In addition, the p-coumarate methyl ester is derived from bio-based lignin, so that the method is environment-friendly and easy to obtain. Meanwhile, in the acrylic resin, hexafluorobutyl methacrylate is also introduced, and the introduction of C-F bonds can improve the weather resistance of the acrylic resin, only the consumption is needed to be paid attention, the mass ratio of the acrylic resin is not more than 8%, and the influence on the viscosity and the adhesive force of the acrylic resin is avoided.
The bonding aid PMMA (polymethyl methacrylate) is modified by adopting 2, 3-pentafluoropropyl acrylate, so that the chemical resistance is improved, and meanwhile, the bonding force between the PMMA bonding aid and the PVDF fluorocarbon resin layer is improved. The PVDF contains-CF 2 -groups in the molecular chain, while the 2, 3-pentafluoropropyl acrylate contains pentafluoropropyl (-CF 2CF2CF3) which has similar polarity with the fluorocarbon chain of PVDF, and the pentafluoropropyl introduced in the PMMA chain segment through copolymerization modification can form stronger intermolecular binding force with PVDF through fluorine-fluorine interaction, so that phase separation is effectively reduced. And the 2, 3-pentafluoropropylacrylate contains acrylate groups, can be highly copolymerized with PMMA, and the obtained modified PMMA can also maintain a high bonding effect with an acrylic resin layer. Therefore, the introduction of the 2, 3-pentafluoropropyl acrylate not only improves the chemical resistance of the PMMA bonding aid, but also improves the bonding effect inside the double-layer powder coating, thereby laying a solid foundation for the large-scale popularization and application of the double-layer powder coating market.
Preferably, the p-coumarate methyl ester is prepared by the following method:
a. Cleaning and crushing raw bagasse, extracting to obtain lignin by adopting a Soxhlet extraction method, then carrying out alkaline hydrolysis in a high-pressure reaction kettle, carrying out acid precipitation treatment, and purifying to obtain p-coumaric acid;
b. Adding thionyl chloride and DMF into the obtained p-coumaric acid, heating, stirring for reaction until the solid is completely dissolved, distilling under reduced pressure to obtain p-coumaric acid chloride, dissolving in methanol, ice-bathing, dropwise adding methanol, slowly heating to room temperature for reaction, distilling under reduced pressure after the reaction is finished, extracting, and recrystallizing to obtain p-coumaric acid methyl ester.
By adopting the scheme, the p-coumarate methyl ester can be extracted and prepared from the waste bagasse, the raw materials are easy to obtain, the preparation method is simple, and the ultraviolet resistance of the modified acrylic resin can be obviously improved.
Preferably, alkaline hydrolysis is carried out in a high-pressure reaction kettle by using 3 percent by weight of sodium hydroxide and an antioxidant Na 2SO3, then the pH is regulated to 2.2 by using 18 percent by weight of hydrochloric acid, standing and precipitating for 10 to 15 hours, centrifuging and purifying to obtain p-coumaric acid;
In the step b, heating to 50-60 ℃, stirring and reacting for 3 hours until the solid is completely dissolved, distilling under reduced pressure to obtain paracoumaroyl chloride, dissolving in methanol, cooling to 0-5 ℃ in an ice bath, dropwise adding methanol, and slowly heating to room temperature for reacting for 5 hours;
The mol ratio of the p-coumaric acid to the thionyl chloride, the DMF and the methanol is 1:1.3:0.1:5.
Preferably, the modified PMMA is prepared by uniformly mixing MMA, 2, 3-pentafluoropropylacrylate, adding tetrahydrofuran, adding an initiator, stirring until the mixture is completely dissolved, introducing nitrogen for deoxidization, heating, preserving heat, reacting, cooling, adding methanol, filtering, washing, and vacuum drying to obtain granular modified PMMA.
Preferably, the 2, 3-pentafluoropropyl acrylate is added in an amount of 0.5 to 3% by mass of the total modified PMMA.
The preparation method is simple and efficient, the addition amount of the 2, 3-pentafluoropropyl acrylate is proper, and tetrahydrofuran is used as a solvent, so that the dispersion effect of the 2, 3-pentafluoropropylacrylate can be improved, and the prepared modified PMMA has better bonding effect.
Preferably, in the preparation process of the modified PMMA, an initiator is azo-bis-isobutyronitrile, nitrogen is introduced for 20min to deoxidize, the temperature is slowly raised to 60-65 ℃, the temperature is kept for 1-2 hours, the temperature is raised to 75-80 ℃, the constant temperature reaction is carried out for 6-8 hours, the temperature is reduced to below 38 ℃, methanol is added, the filtration is carried out, the methanol is used for washing for 2-4 times, and the 50 ℃ vacuum drying is carried out for 24 hours, thus obtaining the granular modified PMMA.
Preferably, in the step S2, the premix is transferred to a reaction kettle, N 2 is introduced to remove air cleanly, the temperature is raised to 80-88 ℃, an initiator is slowly added dropwise, the temperature is kept for 4-6 hours, the temperature is reduced to 50-60 ℃, a neutralizing agent ammonia water is added, the pH is adjusted to 7-8, unreacted impurities are removed by filtration, and the modified acrylic resin is obtained by drying and crushing.
Preferably, in the premix, the mass ratio of the p-coumarate methyl ester is 5-15%.
Preferably, in the step S3, the modified acrylic resin, the curing agent, the surface smoothing agent and the filler are uniformly mixed, and melt-kneaded and extruded by a melt extruder, wherein the temperature of the region I of the melt extruder is set to 105 ℃, and the temperature of the region II of the melt extruder is set to 95 ℃. The temperature is the preferred temperature, and the temperature of the I zone and the II zone of the extruder can be adjusted according to the proportion of materials.
Preferably, in the step S4, PVDF fluorocarbon resin and filler are placed into a reaction kettle, stirred for 15min, heated to 95-120 ℃, stirred for 10-20min under heat preservation, the temperature is adjusted to 80-100 ℃, a surface smoothing agent and an accelerator are added, stirred for 10-20min under heat preservation, a material B is obtained, the temperature is adjusted to 60-80 ℃, a material A and modified PMMA are added, stirred for 20-40min under heat preservation, fed into a feeding machine, uniformly mixed, cooled and tabletted, subjected to multistage crushing, controlled nitrogen pressure of 0.7MPa, flow rate of 5-10m 2/min, screened, and subjected to spheroidization, thus obtaining powder particles with particle size of 5-35 microns.
Through adopting multistage crushing to control nitrogen pressure 0.7MPa, flow 5-10m 2/min, and then better control coating particle size and distribution, promote bilayer powder's packing density, improve the leveling, improve the mixing effect.
Preferably, in the step S1, the solvent is one of propylene glycol methyl ether acetate, toluene and xylene.
Preferably, in the step S2, the initiator is azobisisobutyronitrile or benzoyl peroxide.
Preferably, the curing agent is one of self-sealing isophorone diisocyanate and caprolactam sealing isophorone diisocyanate, the surface smoothing agent is polytetrafluoroethylene, the filler is one of nano silicon dioxide and mica powder, and the accelerator is dibutyl tin laurate.
The invention also provides a fluorocarbon powder coating, which is prepared by adopting the preparation method of the fluorocarbon powder coating, and comprises the following components, by weight, 20-30 parts of PVDF fluorocarbon resin, 1-8 parts of a curing agent, 5-30 parts of a filler, 0.2-2 parts of a surface smoothing agent, 0.5-5 parts of an accelerator, 70-80 parts of modified acrylic resin and 5-10 parts of modified PMMA;
the modified acrylic resin comprises the following raw materials, by weight, 40-65 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 4-10 parts of hydroxyethyl methacrylate, 1-6 parts of hexafluorobutyl methacrylate, 3-10 parts of p-coumaric acid methyl ester, 70-100 parts of a solvent and 0.5-1 part of an initiator;
the modified PMMA comprises, by weight, 90-99 parts of MMA, 0.5-3 parts of 2, 3-pentafluoropropyl acrylate, 50-100 parts of tetrahydrofuran and 0.1-0.6 part of an initiator.
The technical scheme of the invention at least comprises the following beneficial effects:
(1) According to the invention, the methyl p-coumarate is adopted to modify the acrylic resin, so that the methyl p-coumarate has good oxidation resistance, a phenol free radical with stable resonance can be formed, a part of energy in ultraviolet rays is absorbed, and the neutralized free radical is captured, so that the ultraviolet resistance of the acrylic resin is improved, meanwhile, the methyl p-coumarate contains double bonds and has high matching degree between ester groups and acrylate monomers, and free radical copolymerization can be carried out to form a random copolymer, so that the ultraviolet resistance is improved, and meanwhile, the compatibility and other problems are not brought. In addition, the p-coumarate methyl ester is derived from bio-based lignin, so that the method is environment-friendly and easy to obtain.
(2) According to the invention, the powder coating is prepared by adopting a double-layer powder technology, so that a film formed after coating is more prone to gathering a large number of fluorocarbon resin layers (materials B) with higher surface tension on the surface layer, more modified acrylic resin layers (materials A) with lower relative surface tension and higher viscosity are gathered on the bottom, and modified PMMA is adopted as a bonding aid, so that the bonding effect is achieved, meanwhile, the compatibility of the materials A and B is improved, and the occurrence of a layer separation phenomenon is better avoided.
(3) By adopting 2, 3-pentafluoropropylacrylate to modify PMMA, with 2, 3-pentafluoropropylacrylate containing pentafluoropropyl (-CF 2CF2CF3) having similar polarity to the fluorocarbon chain of PVDF, the pentafluoropropyl introduced into the PMMA chain segment through modified copolymerization can form stronger intermolecular binding force with PVDF through fluorine-fluorine interaction, so that phase separation is effectively reduced; and the 2, 3-pentafluoropropylacrylate contains acrylate groups, can be highly copolymerized with PMMA, and the obtained modified PMMA can also maintain a high bonding effect with an acrylic resin layer. Therefore, the introduction of the 2, 3-pentafluoropropyl acrylic ester not only improves the chemical resistance of PMMA bonding aid, but also improves the bonding effect inside the double-layer powder coating, thereby laying a solid foundation for the large-scale popularization and application of the double-layer powder coating market.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which are obtained by a person skilled in the art based on the described embodiments of the invention, fall within the scope of protection of the invention.
The following is a preparation example of methyl p-coumarate.
Preparation example 1
Cleaning and crushing 10 parts of bagasse, adopting a Soxhlet extraction method, adding 50 parts of a mixed solvent of toluene and ethanol mixed according to a ratio of 2:1, extracting lignin for 6 hours, removing fat-soluble impurities, adding 3% wt sodium hydroxide according to a feed liquid ratio of 1:15 (w/v), adding 2 parts of Na 2SO3, performing alkaline hydrolysis in a high-pressure reaction kettle for 3 hours, adopting 18% wt hydrochloric acid to adjust pH to 2.2, standing for precipitation for 10 hours, centrifuging, and purifying to obtain p-coumaric acid. And preparing corresponding reagents according to the mol ratio of p-coumaric acid to thionyl chloride, DMF and methanol of 1:1.3:0.1:5, adding thionyl chloride and DMF (N, N-dimethylformamide) into the obtained p-coumaric acid, heating to 50 ℃, stirring for reacting for 3 hours until the solid is completely dissolved, distilling under reduced pressure to remove excessive thionyl chloride, obtaining p-coumaroyl chloride, dissolving in part of methanol, cooling to 0 ℃ in an ice bath, dropwise adding the rest methanol solution, slowly heating to room temperature for reacting for 5 hours, removing methanol by distilling under reduced pressure after the reaction is finished, extracting by ethyl acetate, and recrystallizing to obtain the p-coumaroyl chloride.
Preparation example 2
Cleaning and crushing 10 parts of bagasse, adopting a Soxhlet extraction method, adding 60 parts of a toluene and ethanol mixed solvent according to a ratio of 2:1, extracting lignin for 6 hours, removing fat-soluble impurities, adding 3% wt sodium hydroxide according to a feed liquid ratio of 1:15 (w/v), adding 1.5 parts of Na 2SO3, performing alkaline hydrolysis in a high-pressure reaction kettle for 3 hours, adopting 18% wt hydrochloric acid to adjust pH to 2.2, standing and precipitating for 15 hours, centrifuging, and purifying to obtain p-coumaric acid. And preparing corresponding reagents according to the mol ratio of p-coumaric acid to thionyl chloride, DMF and methanol of 1:1.3:0.1:5, adding thionyl chloride and DMF (N, N-dimethylformamide) into the obtained p-coumaric acid, heating to 60 ℃, stirring for reacting for 3 hours until the solid is completely dissolved, distilling under reduced pressure to remove excessive thionyl chloride, obtaining p-coumaroyl chloride, dissolving in part of methanol, cooling to 5 ℃ in an ice bath, dropwise adding the rest methanol solution, slowly heating to room temperature for reacting for 5 hours, removing methanol by distilling under reduced pressure after the reaction is finished, extracting by ethyl acetate, and recrystallizing to obtain the p-coumaroyl chloride.
Preparation example 3
The preparation example is different from the preparation example 2 only in that the preparation example is subjected to standing precipitation for 13 hours, thionyl chloride and DMF (N, N-dimethylformamide) are added into the obtained p-coumaric acid, the mixture is heated to 58 ℃ and stirred for reaction for 3 hours until the solid is completely dissolved, the excessive thionyl chloride is removed by reduced pressure distillation, so that p-coumaroyl chloride is obtained, the p-coumaroyl chloride is dissolved in part of methanol, the ice bath is cooled to 2 ℃, and other steps are kept consistent, so that the p-coumaroyl methyl ester is prepared.
The p-coumarate can be prepared by adopting sugarcane waste residues on site, and can also be purchased directly, and the CAS number is 19367-38-5.
The following are examples of fluorocarbon powder coatings. Wherein, the CAS number of the 2, 3-pentafluoropropyl acrylate is 356-86-5, and the CAS number of MMA (hexafluorobutyl methacrylate) is 36405-47-7.
Example 1
Mixing 65 parts of methyl methacrylate, 10 parts of butyl acrylate, 10 parts of hydroxyethyl methacrylate, 6 parts of hexafluorobutyl methacrylate and 10 parts of p-methyl coumarate uniformly, adding 100 parts of propylene glycol methyl ether acetate serving as a solvent, stirring for 10min to obtain a premix, transferring the premix to a reaction kettle, introducing N 2 to remove air completely, heating to 88 ℃, slowly dropwise adding 1 part of Benzoyl Peroxide (BPO) serving as an initiator, preserving heat for 6h, stopping the reaction when the conversion rate is more than 95%, cooling to 60 ℃, adding ammonia water serving as a neutralizer, adjusting the pH to 8, filtering to remove unreacted impurities to obtain a transparent resin solution, drying, and crushing to obtain the modified acrylic resin. Wherein, p-coumarate methyl ester was prepared from preparation example 1.
99 Parts of Methyl Methacrylate (MMA) and 3 parts of 2, 3-pentafluoropropylacrylate are uniformly mixed, 100 parts of Tetrahydrofuran (THF) is added, 0.5 part of Azodiisobutyronitrile (AIBN) serving as an initiator is added, the mixture is stirred until the mixture is completely dissolved, the mixture is aerated for 20min to remove oxygen, the mixture is slowly heated to 60, the mixture is kept for 2 hours, the mixture is heated to 75 ℃ and reacted at the constant temperature for 8 hours, when the conversion rate is more than 95%, the reaction is stopped, the mixture is cooled to 38 ℃ or lower, methanol is added to precipitate a polymer, the polymer is filtered, the polymer is washed for 4 times by using methanol, unreacted monomers and solvents are removed, and the polymer is dried at 50 ℃ in vacuum for 24 hours, so that granular modified PMMA is obtained.
Mixing 80 parts of modified acrylic resin, 6 parts of self-sealing isophorone diisocyanate, 1.5 parts of polytetrafluoroethylene and 20 parts of nano silicon dioxide uniformly, putting into a melt extruder for melt mixing, uniformly dispersing, then melt extruding, tabletting, cooling and finely pulverizing to obtain a material A. Placing 30 parts of PVDF fluorocarbon resin and 8 parts of nano silicon dioxide into a reaction kettle, stirring for 15min, heating to 120 ℃, preserving heat and stirring for 10min, regulating the temperature to 100 ℃, adding 0.5 part of polytetrafluoroethylene and 5 parts of dibutyl tin laurate, preserving heat and stirring for 10min, regulating the temperature to 80 ℃, adding 10 parts of modified PMMA, adding the material A, preserving heat and stirring for 20min, feeding into a forced feeder, uniformly mixing, cooling and tabletting, cooling to room temperature, carrying out multistage crushing, controlling the nitrogen pressure to 0.7MPa, controlling the flow to 10m 2/min, carrying out standard screening, obtaining powder particles with the particle size of 5-35 microns, and carrying out spheroidization treatment to obtain the powder coating.
Example 2
Mixing 40 parts of methyl methacrylate, 20 parts of butyl acrylate, 6 parts of hydroxyethyl methacrylate, 3 parts of hexafluorobutyl methacrylate and 7 parts of p-coumarate uniformly, adding 70 parts of solvent dimethylbenzene, stirring for 10min to obtain a premix, transferring the premix to a reaction kettle, introducing N 2 to remove air completely, heating to 80 ℃, slowly dropwise adding 0.5 part of initiator Azobisisobutyronitrile (AIBN), preserving heat for 4h, when the conversion rate is more than 95%, cooling to 50 ℃, adding neutralizer ammonia water, adjusting the pH to 7, filtering to remove unreacted impurities to obtain a transparent resin solution, drying, and crushing to obtain the modified acrylic resin. Wherein p-coumarate methyl ester was prepared from preparation example 2.
Mixing 90 parts of Methyl Methacrylate (MMA) and 0.5 part of 2, 3-pentafluoropropyl acrylate uniformly, adding 50-100 parts of Tetrahydrofuran (THF), adding 0.1 part of azo-diisobutyronitrile (AIBN) serving as an initiator, stirring until the mixture is completely dissolved, introducing nitrogen for 20min to deoxidize, slowly heating to 65 ℃, preserving heat for 1 hour, heating to 80 ℃, reacting at the constant temperature for 6 hours, stopping the reaction when the conversion rate is more than 95%, cooling to below 38 ℃, adding methanol to precipitate a polymer, filtering, washing 2 times with methanol, removing unreacted monomers and solvents, and drying at 50 ℃ in vacuum for 24 hours to obtain granular modified PMMA.
Mixing 70 parts of modified acrylic resin, 1 part of caprolactam blocked isophorone diisocyanate, 0.1 part of polytetrafluoroethylene and 3 parts of mica powder uniformly, putting into a melt extruder for melt mixing, uniformly dispersing, then melt extruding, tabletting, cooling and finely pulverizing to obtain a material A. Placing 20 parts of PVDF fluorocarbon resin and 2 parts of filler mica powder into a reaction kettle, stirring for 15min, heating to 85 ℃, preserving heat and stirring for 20min, adjusting the temperature to 100 ℃, adding 0.1 part of polytetrafluoroethylene and 1 part of dibutyl tin laurate, preserving heat and stirring for 20min, adjusting the temperature to 50 ℃, adding 5 parts of modified PMMA, adding the A material, preserving heat and stirring for 40min, feeding into a forced feeder, uniformly mixing, cooling and tabletting, cooling to room temperature, carrying out multistage crushing, controlling the nitrogen pressure to 0.7MPa, controlling the flow to 5m 2/min, carrying out standard screening, obtaining powder particles with the particle size of 5-35 microns, and carrying out spheroidization treatment to obtain the powder coating.
Example 3
Mixing 50 parts of methyl methacrylate, 15 parts of butyl acrylate, 8 parts of hydroxyethyl methacrylate, 4 parts of hexafluorobutyl methacrylate and 8 parts of p-coumarate, adding 80 parts of solvent toluene, stirring for 10min to obtain a premix, transferring the premix to a reaction kettle, introducing N 2 to remove air completely, heating to 85 ℃, slowly dropwise adding 0.6 part of initiator Azobisisobutyronitrile (AIBN), preserving heat for 5h, when the conversion rate is more than 95%, cooling to 55 ℃, adding neutralizer ammonia water, adjusting the pH to 8, filtering to remove unreacted impurities to obtain a transparent resin solution, drying, and crushing to obtain the modified acrylic resin. Wherein p-coumarate methyl ester was prepared from preparation example 3.
Mixing 95 parts of Methyl Methacrylate (MMA) and 2 parts of 2, 3-pentafluoropropylacrylate uniformly, adding 90 parts of Tetrahydrofuran (THF), adding 0.3 part of Azodiisobutyronitrile (AIBN) serving as an initiator, stirring until the mixture is completely dissolved, introducing nitrogen for 20min to deoxidize, slowly heating to 60 ℃, preserving the temperature for 1.5 hours, heating to 76 ℃, reacting at the constant temperature for 6 hours, stopping the reaction when the conversion rate is more than 95%, cooling to below 38 ℃, adding methanol to precipitate a polymer, filtering, washing 3 times by using methanol, removing unreacted monomers and solvents, and drying at 50 ℃ in vacuum for 24 hours to obtain granular modified PMMA.
Mixing 75 parts of modified acrylic resin, 5 parts of caprolactam blocked isophorone diisocyanate, 0.6 part of polytetrafluoroethylene and 10 parts of nano silicon dioxide uniformly, putting into a melt extruder for melt mixing, uniformly dispersing, then melt extruding, tabletting, cooling and finely pulverizing to obtain a material A. Placing 25 parts of PVDF fluorocarbon resin and 3 parts of filler nano silicon dioxide into a reaction kettle, stirring for 15min, heating to 110 ℃, preserving heat and stirring for 15min, regulating the temperature to 90 ℃, adding 0.3 part of polytetrafluoroethylene and 2 parts of dibutyl tin laurate, preserving heat and stirring for 15min, regulating the temperature to 60 ℃, adding 8 parts of modified PMMA, adding the A material, preserving heat and stirring for 30min, feeding into a forced feeder, uniformly mixing, cooling and tabletting, cooling to room temperature, carrying out multistage crushing, controlling the nitrogen pressure to 0.7MPa, controlling the flow to 6m 2/min, carrying out standard screening, obtaining powder particles with the particle size of 5-35 microns, and carrying out spheroidization treatment to obtain the powder coating.
Example 4
Mixing 55 parts of methyl methacrylate, 15 parts of butyl acrylate, 8 parts of hydroxyethyl methacrylate, 3 parts of hexafluorobutyl methacrylate and 8 parts of p-coumarate methyl ester uniformly, adding 80 parts of solvent toluene, stirring for 10min to obtain a premix, transferring the premix to a reaction kettle, introducing N 2 to remove air completely, heating to 85 ℃, slowly dropwise adding 0.6 part of initiator Azobisisobutyronitrile (AIBN), preserving heat for 5h, when the conversion rate is more than 95%, cooling to 55 ℃, adding neutralizer ammonia water, adjusting the pH to 8, filtering to remove unreacted impurities to obtain a transparent resin solution, drying, and crushing to obtain the modified acrylic resin. Wherein p-coumarate methyl ester was prepared from preparation example 3.
96 Parts of Methyl Methacrylate (MMA) and 2 parts of 2, 3-pentafluoropropyl acrylate are uniformly mixed, 90 parts of Tetrahydrofuran (THF) is added, 0.3 part of Azodiisobutyronitrile (AIBN) as an initiator is added, the mixture is stirred until the mixture is completely dissolved, nitrogen is introduced for 20min to remove oxygen, the mixture is slowly heated to 60 ℃, the temperature is kept for 1.5 hours, the temperature is raised to 78 ℃, the reaction is kept at the constant temperature for 6 hours, when the conversion rate is more than 95%, the reaction is stopped, the temperature is reduced to below 38 ℃, methanol is added to precipitate a polymer, the polymer is filtered, the polymer is washed 3 times by methanol, unreacted monomers and solvents are removed, and the polymer is dried at 50 ℃ in vacuum for 24 hours, so that granular modified PMMA is obtained.
76 Parts of modified acrylic resin, 5 parts of self-sealing isophorone diisocyanate, 0.6 part of polytetrafluoroethylene and 10 parts of nano silicon dioxide are uniformly mixed, and are put into a melt extruder for melt mixing, uniform dispersion, then melt extrusion, tabletting, cooling and fine crushing are carried out, so that a material A is obtained. Placing 25 parts of PVDF fluorocarbon resin and 3 parts of filler nano silicon dioxide into a reaction kettle, stirring for 15min, heating to 110 ℃, preserving heat and stirring for 15min, regulating the temperature to 90 ℃, adding 0.3 part of polytetrafluoroethylene and 2 parts of dibutyl tin laurate, preserving heat and stirring for 15min, regulating the temperature to 60 ℃, adding 7 parts of modified PMMA, adding the A material, preserving heat and stirring for 30min, feeding into a forced feeder, uniformly mixing, cooling and tabletting, cooling to room temperature, carrying out multistage crushing, controlling the nitrogen pressure to 0.7MPa, controlling the flow to 8m 2/min, carrying out standard screening, obtaining powder particles with the particle size of 5-35 microns, and carrying out spheroidization treatment to obtain the powder coating.
Example 5
Mixing 55 parts of methyl methacrylate, 12 parts of butyl acrylate, 8 parts of hydroxyethyl methacrylate, 2 parts of hexafluorobutyl methacrylate and 8 parts of p-coumarate methyl ester uniformly, adding 80 parts of solvent toluene, stirring for 10min to obtain a premix, transferring the premix to a reaction kettle, introducing N 2 to remove air completely, heating to 85 ℃, slowly dropwise adding 0.6 part of initiator Azobisisobutyronitrile (AIBN), preserving heat for 5h, when the conversion rate is more than 95%, cooling to 55 ℃, adding neutralizer ammonia water, adjusting the pH to 8, filtering to remove unreacted impurities to obtain a transparent resin solution, drying, and crushing to obtain the modified acrylic resin. Wherein p-coumarate methyl ester was prepared from preparation example 2.
97 Parts of Methyl Methacrylate (MMA) and 2 parts of 2, 3-pentafluoropropylacrylate are uniformly mixed, 92 parts of Tetrahydrofuran (THF) is added, 0.3 part of Azodiisobutyronitrile (AIBN) as an initiator is added, the mixture is stirred until the mixture is completely dissolved, the mixture is aerated for 20min to remove oxygen, the mixture is slowly heated to 60 ℃, the temperature is kept for 1.5 hours, the mixture is heated to 78 ℃ and reacts at the constant temperature for 6 hours, when the conversion rate is more than 95%, the reaction is stopped, the temperature is reduced to below 38 ℃, methanol is added to precipitate a polymer, the polymer is filtered, the polymer is washed 3 times by methanol, unreacted monomers and solvents are removed, and the polymer is dried at 50 ℃ in vacuum for 24 hours, so that granular modified PMMA is obtained.
Mixing 75 parts of modified acrylic resin, 4 parts of self-sealing isophorone diisocyanate, 0.8 part of polytetrafluoroethylene and 10 parts of nano silicon dioxide uniformly, putting into a melt extruder for melt mixing, uniformly dispersing, then melt extruding, tabletting, cooling and finely pulverizing to obtain a material A. 26 parts of PVDF fluorocarbon resin and 3 parts of filler nano silicon dioxide are put into a reaction kettle, stirred for 15min, heated to 110 ℃, stirred for 15min with heat preservation, the temperature is adjusted to 93 ℃,0.3 part of polytetrafluoroethylene and 2 parts of dibutyl tin laurate are added, stirred for 15min with heat preservation, the temperature is adjusted to 60 ℃, 8 parts of modified PMMA are added, then the A material is added, stirred for 30min with heat preservation, fed into a forced feeder, uniformly mixed, cooled and tableted, cooled to room temperature, subjected to multistage crushing, controlled to nitrogen pressure of 0.7MPa, flow rate of 6m 2/min, subjected to standard screening, and subjected to spheroidization, thus obtaining powder particles with particle size of 5-35 microns.
The present invention also performs the following comparative examples and related experiments
Comparative example 1
The powder coating was prepared in the same manner as in example 4 except that methyl methacrylate was used instead of methyl p-coumarate, i.e., the amount of methyl methacrylate added in the preparation of the modified acrylic resin was 63 parts, and other components and preparation processes were identical to those of example 4.
Comparative example 2
The only difference from example 4 is that the conventional nano zinc oxide was used instead of methyl p-coumarate, and other components and preparation processes were the same as those of example 4, to prepare a powder coating.
Comparative example 3
The only difference from example 4 is that the preparation of modified PMMA is not carried out, but instead of conventional PMMA, other components and preparation processes are identical to those of example 4, and a powder coating is prepared.
Performance test
The powder coatings obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to weather resistance, salt spray resistance, adhesion, hardness, ultraviolet light resistance and oxidation resistance tests according to the following criteria.
(One) weather resistance test
According to the detection method, the artificial weather aging performance is 1000H, irradiance is 0.51 (W/m 2 @340 nm), BST is 65 ℃, the temperature in a box is 38 ℃, humidity in the box is 50% RH, stage 1 is illumination, 102min, stage 2 is illumination, 18min, the front surface of a sprayed sample is subjected to total test time is 1000H, and the result is that discoloration is less than or equal to 2 levels, light loss is less than or equal to 2 levels, and abnormal phenomena such as pulverization, bubbles, cracking and stripping are avoided. The test results were finally summarized as shown in table 1 below.
(II) salt spray resistance test
The detection method refers to the standard GB/T10125-2021, the salt spray resistance 900H is detected, an intelligent salt spray corrosion test box is adopted, the instrument number E-033-011TD is adopted, the result is that the one-way corrosion at the scribing position is less than or equal to 2.0mm, and the non-scribing area is free of abnormality. The final test results are summarized in table 1 below.
TABLE 1
From the test results in table 1 above, it is evident that the powder coating products obtained in examples 1 to 5 prepared by the present invention have excellent artificial weathering resistance and salt spray resistance, and can meet the requirements of high weather resistance and salt spray resistance of high-end buildings and ships.
The test results of comparative examples 2 to 3 show that the powder coating obtained in comparative example 2 is added with metal oxide to resist salt rust, but has poor compatibility and poor adhesive force, and has slight local peeling, while the powder coating obtained in comparative example 3 has insufficient bonding force due to the bonding aid, cannot withstand long-time weather resistance and salt fog resistance tests, is easy to generate local aging and delamination, has slight foaming and even cracking, and cannot meet the requirements of high-performance coating products.
(III) adhesion test
The detection method refers to standard GB/T9286-2021 for adhesion test, an instrument coating adhesion tester is adopted, instrument numbers E-008-011TD are adopted, detection conditions are (23+/-2) DEGC, (50+/-5)%, 16h, square grids are divided, the dividing distance is 2mm, the dividing line number in each direction is 6, the adhesive tape type is 3M 600, the adhesive tape stripping angle is 60 DEG, the material type is hard, and the result is less than or equal to 1 level. The final test results are summarized in table 2 below.
(IV) hardness (scratch) test
The detection method refers to standard GB/T6739-2022 for hardness (scratch) test, and the fluorocarbon powder coating is subjected to detection before 1000H of artificial weather aging resistance and detection after 1000H of artificial weather aging resistance, and the technical requirement is that the hardness is more than 1H. The final test results are summarized in table 2 below.
(V) ultraviolet resistance test
The detection method refers to the standard GB/T1865-2009, and the detection result evaluation standard is whether color is changed or not, and the technical requirement is that the color is not changed. The final test results are summarized in table 2 below.
Sixth test for Oxidation resistance
The detection method refers to the standard GB/T1766-2008, and the detection result evaluation standard is whether the chalking phenomenon occurs or not, and the technical requirement is that the chalking is not performed. The final test results are summarized in table 2 below.
TABLE 2
From the test results in Table 2 above, it is apparent that the powder coating products obtained in examples 1 to 5 prepared by the present invention have excellent adhesion, hardness, and ultraviolet light resistance and oxidation resistance, and can meet the requirements of high-performance powder coatings.
As can be seen from the test results of comparative examples 1-2, the powder coating obtained in comparative example 1 is excellent in adhesion properties, but poor in ultraviolet resistance and oxidation resistance, and the hardness after aging is also reduced, which means that the modification of the methyl coumarate on the acrylic resin can obviously improve ultraviolet resistance and oxidation resistance, and further has an influence on the aging hardness performance for a long time. The powder coating of comparative example 2, though improving the ultraviolet light resistance due to the addition of the metal oxide, has poor compatibility, affects the adhesion of the product, and cannot meet the requirements of high-performance coating products.
The foregoing is a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
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| JP6204519B2 (en) * | 2016-03-08 | 2017-09-27 | 互応化学工業株式会社 | Photosensitive resin composition, dry film, and printed wiring board |
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| CN114292185B (en) * | 2021-12-14 | 2022-12-06 | 华南理工大学 | Method for preparing p-coumaric acid ester by catalyzing lignin depolymerization through ionic liquid |
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| CN108047836A (en) * | 2017-12-29 | 2018-05-18 | 广东华江粉末科技有限公司 | A kind of extra-weather-proof PVDF double layer of powder coating and preparation method thereof |
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