Soluble polyarylether oil paint and application thereof

Abstract

The invention discloses a soluble polyarylether oil paint and application thereof. The soluble polyarylether oil paint comprises 5-15 phr of soluble polyarylether, 3-10 phr of a lubricant, 50-80 phr of an organic solvent, 1-10 phr of a dispersant, 0.1-5 phr of an anti-settling agent, 0.1-5 phr of an antifoaming agent, 0.1-3 phr of a leveling agent and 0.1-2 phr of a coupling agent. Wherein the soluble polyarylether is prepared from a cyano-containing dihalogen monomer A, a dihalogen monomer B and a distorted non-coplanar monomer, the dispersing agent is prepared from phenolphthalein, 4, 4 '-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent, and the lubricant is a fluorine-containing lubricant. The specific dispersing agent prepared from phenolphthalein, 4, 4 '-difluorobenzophenone and hexafluorobisphenol A is adopted, the fluorine-containing lubricant is stably dispersed in the coating by using the dispersing agent, and the problem that the lubricant in the soluble polyarylether oil coating is difficult to disperse is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to a soluble polyarylether oily coating and an application thereof. Background Art

[0002] Conventional polyarylene ether resins are insoluble in organic solvents, such as N-methylpyrrolidone, and therefore cannot be applied as coatings using air spray. While the addition of phenolphthalein to the preparation of polyarylene ether resins improves their solubility in organic solvents, it requires the use of a lubricant during the coating preparation process, which is difficult to evenly disperse in soluble polyarylene ether coatings. Summary of the Invention

[0003] In order to overcome the problems in the prior art, the present invention provides a soluble polyarylene ether oily coating and its application, and prepares a dispersant for the lubrication in the soluble polyarylene ether oily coating to improve the problem of difficulty in dispersing the lubricant in the soluble polyarylene ether oily coating.

[0004] In order to solve the above technical problems, the technical solution proposed by the present invention is: The present invention provides a soluble polyarylether oily paint, comprising the following raw materials in parts by weight: Soluble polyarylether 5-15phr, lubricant 3-10phr, organic solvent 50-80phr, dispersant 1-10phr, anti-settling agent 0.1-5phr, defoamer 0.1-5phr, leveling agent 0.1-3phr and coupling agent 0.1-2phr; The soluble polyarylether is prepared from a cyano-containing dihalogen monomer A, a dihalogen monomer B and a twisted non-coplanar monomer; the dispersant is prepared from phenolphthalein, 4,4'-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent; and the lubricant is a fluorine-containing lubricant.

[0005] In the present invention, a twisted non-coplanar structure is introduced into the polyarylene ether resin, so that the polyarylene ether resin can be dissolved in an organic solvent to prepare a solvent-based coating. Since lubricants and dispersants are key additives for coatings, the lubricant used in the present invention is a fluorine-containing lubricant. At the same time, combined with the molecular structure of the soluble polyarylene ether, the present invention adopts a dispersant prepared from phenolphthalein, 4,4'-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent. The fluorine-containing part of the dispersant is wrapped on the surface of the lubricant, and the polar functional group structure can form an electric charge on the surface of the lubricant, preventing other lubricants from agglomerating, and can effectively disperse the lubricant in the coating system.

[0006] As an optional embodiment, in the coating provided by the present invention, the twisted non-coplanar monomer is selected from one or more of 1,4-cyclohexanedimethanol, phenolphthalein, 3,3-(2,4-diamino-6,7-pterydine-diyl)diphenol, phenolphthalein, 1,5-naphthalenediol, 2,5-triptylidenediol, 9,9'-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-isopropyl-4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxy-1-naphthyl)phthalide, 9,9'-bis(4-hydroxyphenyl)xanthene, and 9,9'-bis(3-nitro-4-hydroxyphenyl)xanthene.

[0007] As an optional embodiment, in the coating provided by the present invention, the cyano group-containing dihalogen monomer A is selected from 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile; the structural formula of the dihalogen monomer B is as follows: .

[0008] In the present invention, the addition of 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile can form hydrogen bonds and chemical bonds with the metal plate, and can improve the adhesion between the coating and the metal substrate at the molecular level.

[0009] In the present invention, the cyano-containing dihalogen monomer A has an Ar1 structure in the polymer chain, the dihalogen monomer B has an Ar2 structure in the polymer chain, and the structural formula of the polyarylene ether molecular chain is as follows: .

[0010] As an optional embodiment, in the coating provided by the present invention, the ratio of the molar number of the twisted non-coplanar monomer to the total molar number of the cyano-containing dihalogen monomer A and the dihalogen monomer B in the soluble polyarylene ether is 1:1; the molar number of the cyano-containing dihalogen monomer A accounts for 10%-90% of the total molar number of the cyano-containing dihalogen monomer A and the dihalogen monomer B; the ratio of the sum of the mass of the twisted non-coplanar monomer, the cyano-containing dihalogen monomer A, and the dihalogen monomer B to the mass of the catalyst is 1:(0.8~1.8).

[0011] As an optional embodiment, in the coating provided by the present invention, a catalyst and a water-carrying agent are further added during the preparation of the soluble polyarylene ether, and the molar ratio of the twisted non-coplanar monomer to the catalyst is 1:(0.8~1.8).

[0012] As an optional embodiment, in the coating provided by the present invention, the solvent used in the preparation process of the soluble polyarylene ether is selected from one of N-methylpyrrolidone (NMP) and sulfolane (TMS), or a mixture of the two.

[0013] As an optional embodiment, in the coating provided by the present invention, the molar number of phenolphthalein in the dispersant accounts for 25%-75% of the total molar number of phenolphthalein and hexafluorobisphenol A; and the ratio of the sum of the molar numbers of phenolphthalein and hexafluorobisphenol A monomers to the molar number of the catalyst is 1:(0.8~1.8).

[0014] As an optional embodiment, in the coating provided by the present invention, the catalyst is an alkali metal carbonate.

[0015] As an optional embodiment, in the coating provided by the present invention, the water-carrying agent is selected from one or both of toluene and xylene.

[0016] As an optional embodiment, in the coating provided by the present invention, the organic solvent is selected from one or more of chloroform, 1,2-dichloroethane, tetrahydrofuran, cyclohexanone, N,N-dimethylamide, N-methylpyrrolidone, and N,N-dimethylacetamide.

[0017] As an optional embodiment, in the coating provided by the present invention, the anti-settling agent is selected from one or more of silicone anti-settling agents, silica, and natural montmorillonite.

[0018] As an optional embodiment, in the coating provided by the present invention, the defoaming agent is selected from one or more of modified polysiloxanes, non-silicon organic polymers, and acrylates.

[0019] As an optional embodiment, in the coating provided by the present invention, the leveling agent is selected from one or more of acrylate copolymers, silicon-modified polyacrylates, and modified polysiloxanes.

[0020] As an optional embodiment, in the coating provided by the present invention, the coupling agent is selected from one or more of a silane coupling agent (aminosilane coupling agent, epoxysilane coupling agent, sulfur-based silane coupling agent), a titanate coupling agent, an aluminate coupling agent, and an aluminum-titanium composite coupling agent.

[0021] As an optional embodiment, in the coating provided by the present invention, the soluble polyarylether oil-based coating further comprises a pigment, and the pigment is selected from one or more of carbon black, titanium dioxide, iron oxide red, chrome yellow, and lead chrome green.

[0022] As an optional embodiment, in the coating provided by the present invention, the preparation method of the dispersant comprises the following steps: Phenolphthalein, 4,4'-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent are added to a reaction solvent. Under heating conditions, the water-carrying agent is used to carry water, and then the water-carrying agent is removed and the heating is continued to react. As the viscosity of the reaction solution increases, the solvent is gradually added dropwise. When the viscosity of the system no longer increases, the solvent is added to adjust the system mass fraction to 30wt%, the temperature is lowered to stop the reaction, and the reaction solution is poured into a dilute acid solution to terminate the reaction to obtain a fibrous polymer, which is then treated to obtain the dispersant. The chemical reaction for preparing the dispersant is as follows:

[0023] As an optional embodiment, in the coating provided by the present invention, the temperature of the water is 130-160° C., and the time is 2-5 hours; the heating temperature is 180-210° C., and the time is 6-20 hours.

[0024] As an optional embodiment, in the coating provided by the present invention, the treatment process includes: crushing the fibrous polymer, washing it thoroughly with water and ethanol, and then drying it.

[0025] Based on the same technical concept, the present invention also provides the application of the above-mentioned soluble polyarylene ether oily coating on the surface of a metal substrate, wherein the metal substrate is selected from one of iron plate, steel plate, aluminum plate or copper plate, and the coating method is spraying.

[0026] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention introduces a twisted non-coplanar structure into the polyarylene ether polymer chain, making the polyarylene ether polymer soluble in a polar organic solvent. The soluble polyarylene ether resin is prepared into a coating, which is convenient for spraying. At the same time, a specific dispersant prepared from phenolphthalein, 4,4'-difluorobenzophenone and hexafluorobisphenol A is used to stably disperse the fluorinated lubricant in the coating to prevent the lubricant from agglomerating.

[0027] (2) The soluble polyarylether oil-based coating prepared in the present invention introduces a cyano functional group to increase the polarity of the molecular chain and improve the bonding force between the coating and the metal. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0029] Figure 1 This is the infrared detection result of the dispersant prepared in Example 1. DETAILED DESCRIPTION

[0030] In order to facilitate understanding of the present invention, the present invention will be described more comprehensively and meticulously below in combination with the specification and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0031] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0032] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0033] Example 1 Preparation of soluble polyarylene ether: Using a 250 mL polymerization reactor as an example, the following raw materials were prepared: twisted non-coplanar monomer phenolphthalein (20 mmol), 4,4-difluorobenzophenone (10 mmol), 2,6-difluorobenzonitrile (10 mmol), catalyst sodium carbonate (28 mmol), water-carrying agent toluene (40 mL), and reaction solvent sulfolane (30 mL). Nitrogen was then introduced into the reaction system, and cooling water was passed through the condenser. The temperature was slowly raised to 140°C for azeotropic dehydration. The reaction was refluxed for 4 hours, and then the temperature was raised to 200°C. During this time, the water-carrying agent and water mixture was removed, and polymerization began. During this period, the viscosity of the polymerization system gradually increased. Based on the system's behavior, an appropriate amount of reaction solvent was added until the viscosity stopped increasing. 40 mL of solvent was then added to dilute the mixture and rapidly stirred. The polymer mixture was slowly poured into a dilute acid solution, resulting in the precipitation of a white, fibrous polymer. The mixture was then washed repeatedly with ethanol and water to obtain the soluble polyarylene ether.

[0034] Preparation of the dispersant: Using a 250 mL polymerization reactor as an example, prepare the following raw materials: phenolphthalein (10 mmol), hexafluorobisphenol A (10 mmol), 4,4-difluorobenzophenone (20 mmol), potassium carbonate catalyst (28 mmol), toluene (40 mL), and sulfolane (30 mL). Nitrogen is then introduced into the reaction system, cooling water is passed through the condenser, and the temperature is slowly raised to 140°C for azeotropic dehydration. The reaction is then refluxed for 4 hours, and then raised to 200°C. The mixture of the water-carrying agent and water is then removed, and the polymerization reaction begins. During this period, the viscosity of the polymerization system will gradually increase. Depending on the system's behavior, an appropriate amount of reaction solvent is added until the viscosity stops rising. 40 mL of solvent is then added to dilute the mixture and rapidly stirred. The polymer mixture is slowly poured into a dilute acid solution to precipitate a fibrous polymer. This is then washed repeatedly with ethanol and water to yield a fluorinated polar poly(aryletherketone), the dispersant.

[0035] The prepared dispersant was subjected to infrared detection, and the results were as follows: Figure 1 As shown, after infrared detection at 1171cm -1 The absorption peak of -CF3 is 1649cm -1 The characteristic absorption peak of the carbonyl group of the ketone group is at 1716 cm -1 , indicating that the dispersant of the present invention has been prepared.

[0036] Preparation of a soluble polyarylene ether coating: Prepare raw materials, wherein the soluble polyarylene ether prepared above is used in an amount of 14 phr, the lubricant polytetrafluoroethylene is used in an amount of 6 phr, the organic solvent N-methylpyrrolidone is used in an amount of 74.7 phr, the dispersant prepared above is used in an amount of 3.6 phr, the anti-settling agent is used in an amount of 0.5 phr, the defoamer is used in an amount of 0.5 phr, the leveling agent is used in an amount of 0.1 phr, the coupling agent is used in an amount of 0.5 phr, and the pigment is used in an amount of 0.1 phr. The coating is micro-nano-grinded using a planetary ball mill, and the grinding process is as follows: a rotation speed of 100-3000 rpm, a revolution speed of 50-2000 rpm, forward stirring for 30-60 minutes, reverse stirring for 30-60 minutes, and a cycle of 2-4 times. The ratio of the mass of the ball milling beads to the total mass of the coating is 0.1-2, and the ball milling beads and the material account for 0.5-0.9 of the total volume of the ball milling jar. After micro-nano dispersion, a soluble polyarylene ether coating is obtained. After the base material is cleaned, the base surface is dried and preheated, and then air sprayed on the base surface and the coating is cured at high temperature to obtain a coating.

[0037] Example 2 Preparation of soluble polyarylene ether: Using a 250 mL polymerization reactor as an example, the following raw materials were prepared: twisted non-coplanar monomers 1,4-cyclohexanedimethanol (20 mmol), 4,4-difluorodiphenyl sulfone (2 mmol), 2,6-difluorobenzonitrile (18 mmol), catalyst sodium carbonate (14 mmol), water-carrying agent xylene (40 mL), and reaction solvent N-methylpyrrolidone (30 mL). Nitrogen was then introduced into the reaction system, cooling water was passed through the condenser, and the temperature was slowly raised to 130°C for azeotropic dehydration. The reaction was then refluxed for 2 hours and then raised to 180°C. During this time, the water-carrying agent and water mixture was removed, and polymerization began. During this period, the viscosity of the polymerization system gradually increased. Depending on the system's behavior, an appropriate amount of reaction solvent was added until the viscosity stopped rising. 40 mL of solvent was then added to dilute the mixture and rapidly stirred. The polymer mixture was slowly poured into a dilute acid solution, resulting in the precipitation of a white, fibrous polymer. The mixture was then washed repeatedly with ethanol and water to obtain the soluble polyarylene ether.

[0038] Preparation of the dispersant: Using a 250mL polymerization reactor as an example, prepare the following raw materials: phenolphthalein (4 mmol), hexafluorobisphenol A (16 mmol), 4,4-difluorobenzophenone (20 mmol), potassium carbonate catalyst (14 mmol), xylene (40 mL), and N-methylpyrrolidone (30 mL). Nitrogen is then introduced into the reaction system, cooling water is passed through the condenser, and the temperature is slowly raised to 130°C for azeotropic dehydration. The reaction is then refluxed for 2 hours, and then raised to 180°C. During this time, the mixture of the water-carrying agent and water is removed, and the polymerization reaction begins. During this period, the viscosity of the polymerization system will gradually increase. Depending on the system's behavior, an appropriate amount of reaction solvent is added until the viscosity stops rising. Then, 40 mL of solvent is added to dilute the mixture and rapidly stirred. The polymer mixture is slowly poured into a dilute acid solution to precipitate a fibrous polymer.

[0039] Preparation of a soluble polyarylene ether coating: Prepare raw materials, wherein the soluble polyarylene ether prepared above is used in an amount of 14 phr, the lubricant polytetrafluoroethylene is used in an amount of 6 phr, the organic solvent N-methylpyrrolidone is used in an amount of 74.7 phr, the dispersant prepared above is used in an amount of 3.6 phr, the anti-settling agent is used in an amount of 0.5 phr, the defoamer is used in an amount of 0.5 phr, the leveling agent is used in an amount of 0.1 phr, the coupling agent is used in an amount of 0.5 phr, and the pigment is used in an amount of 0.1 phr. The coating is micro-nano-grinded using a planetary ball mill, and the grinding process is as follows: a rotation speed of 100-3000 rpm, a revolution speed of 50-2000 rpm, forward stirring for 30-60 minutes, reverse stirring for 30-60 minutes, and a cycle of 2-4 times. The ratio of the mass of the ball milling beads to the total mass of the coating is 0.1-2, and the ball milling beads and the material account for 0.5-0.9 of the total volume of the ball milling jar. After micro-nano dispersion, a soluble polyarylene ether coating is obtained. After the base material is cleaned, the base surface is dried and preheated, and then air sprayed on the base surface and the coating is cured at high temperature to obtain a coating.

[0040] Example 3 Preparation of soluble polyarylene ether: Using a 250 mL polymerization reactor as an example, the following raw materials were prepared: twisted non-coplanar monomer phenolphthalein (20 mmol), 4,4-difluorotriphenyldimethyl ketone (18 mmol), 2,6-dichlorobenzonitrile (2 mmol), catalyst potassium carbonate (14 mmol), water-carrying agent xylene (40 mL), and reaction solvent sulfolane (30 mL). Nitrogen was then introduced into the reaction system, cooling water was passed through the condenser, and the temperature was slowly raised to 160°C for azeotropic dehydration. The reaction was then refluxed for 2 hours, and then raised to 210°C. During this time, the water-carrying agent and water mixture was removed, and polymerization began. During this period, the viscosity of the polymerization system gradually increased. Based on the system's behavior, an appropriate amount of reaction solvent was added until the viscosity stopped rising. 40 mL of solvent was then added to dilute the mixture and rapidly stirred. The polymer mixture was slowly poured into a dilute acid solution, resulting in the precipitation of a white, fibrous polymer. The mixture was then washed repeatedly with ethanol and water to obtain the soluble polyarylene ether.

[0041] Preparation of the dispersant: Using a 250mL polymerization reactor as an example, prepare the following raw materials: phenolphthalein (16 mmol), hexafluorobisphenol A (4 mmol), 4,4-difluorobenzophenone (20 mmol), potassium carbonate catalyst (14 mmol), toluene (40 mL), and sulfolane (30 mL). Nitrogen is then introduced into the reaction system, cooling water is passed through the condenser, and the temperature is slowly raised to 160°C for azeotropic dehydration. The reaction is then refluxed for 2 hours, and then raised to 210°C. During this time, the mixture of the water-entraining agent and water is removed, and the polymerization reaction begins. During this period, the viscosity of the polymerization system will gradually increase. Depending on the system's behavior, an appropriate amount of reaction solvent is added until the viscosity stops rising. Then, 40 mL of solvent is added to dilute the mixture and rapidly stirred. The polymer mixture is slowly poured into a dilute acid solution to precipitate a fibrous polymer.

[0042] Preparation of a soluble polyarylene ether coating: Prepare raw materials, wherein the soluble polyarylene ether prepared above is used in an amount of 14 phr, the lubricant polytetrafluoroethylene is used in an amount of 6 phr, the organic solvent N-methylpyrrolidone is used in an amount of 74.7 phr, the dispersant prepared above is used in an amount of 3.6 phr, the anti-settling agent is used in an amount of 0.5 phr, the defoamer is used in an amount of 0.5 phr, the leveling agent is used in an amount of 0.1 phr, the coupling agent is used in an amount of 0.5 phr, and the pigment is used in an amount of 0.1 phr. The coating is micro-nano-grinded using a planetary ball mill, and the grinding process is as follows: a rotation speed of 100-3000 rpm, a revolution speed of 50-2000 rpm, forward stirring for 30-60 minutes, reverse stirring for 30-60 minutes, and a cycle of 2-4 times. The ratio of the mass of the ball milling beads to the total mass of the coating is 0.1-2, and the ball milling beads and the material account for 0.5-0.9 of the total volume of the ball milling jar. After micro-nano dispersion, a soluble polyarylene ether coating is obtained. After the base material is cleaned, the base surface is dried and preheated, and then air sprayed on the base surface and the coating is cured at high temperature to obtain a coating.

[0043] Example 4 Preparation of soluble polyarylene ether: Using a 250 mL polymerization reactor as an example, the following raw materials were prepared: twisted non-coplanar monomer 9,9'-bis(4-hydroxyphenyl)fluorene (20 mmol), 4,4-difluorobenzophenone (10 mmol), 2,6-difluorobenzonitrile (10 mmol), catalyst potassium carbonate (28 mmol), water-carrying agent toluene (40 mL), and reaction solvent sulfolane (30 mL). Nitrogen was then introduced into the reaction system, cooling water was passed through the condenser, and the temperature was slowly raised to 140°C for azeotropic dehydration. The reaction was then refluxed for 4 hours and then raised to 200°C. During this time, the water-carrying agent and water mixture was removed, and polymerization began. During this period, the viscosity of the polymerization system gradually increased. Based on the system's behavior, an appropriate amount of reaction solvent was added until the viscosity stopped rising. 40 mL of solvent was then added to dilute the mixture and rapidly stirred. The polymer mixture was slowly poured into a dilute acid solution, resulting in the precipitation of a white, fibrous polymer. The mixture was then washed repeatedly with ethanol and water to obtain the soluble polyarylene ether.

[0044] Preparation of the dispersant: Using a 250 mL polymerization reactor as an example, prepare the following raw materials: phenolphthalein (10 mmol), hexafluorobisphenol A (10 mmol), 4,4-difluorobenzophenone (20 mmol), potassium carbonate catalyst (28 mmol), toluene (40 mL), and sulfolane (30 mL). Nitrogen is then introduced into the reaction system, cooling water is passed through the condenser, and the temperature is slowly raised to 140°C for azeotropic dehydration. The reaction is then refluxed for 4 hours, and then raised to 200°C. During this time, the mixture of the water-carrying agent and water is removed, and the polymerization reaction begins. During this period, the viscosity of the polymerization system will gradually increase. Depending on the system's behavior, an appropriate amount of reaction solvent is added until the viscosity stops rising. 40 mL of solvent is then added to dilute the mixture and rapidly stirred. The polymer mixture is slowly poured into a dilute acid solution to precipitate a fibrous polymer. This is then washed repeatedly with ethanol and water to yield a fluorinated polar poly(aryletherketone), the dispersant.

[0045] Preparation of a soluble polyarylene ether coating: Prepare raw materials, including 15 phr of soluble polyarylene ether, 3 phr of lubricant polytetrafluoroethylene, 72.7 phr of organic solvent N-methylpyrrolidone, 1 phr of the dispersant prepared above, 5 phr of anti-settling agent, 0.1 phr of defoamer, 3 phr of leveling agent, 0.1 phr of coupling agent, and 0.1 phr of pigment. The coating is micro-nano-milled using a planetary ball mill. The milling process is as follows: a rotation speed of 100-3000 rpm, an orbital speed of 50-2000 rpm, forward stirring for 30-60 minutes, reverse stirring for 30-60 minutes, and a cycle of 2-4 times. The ratio of ball mill mass to total coating mass is 0.1-2, and the ball mill mass and material account for 0.5-0.9 of the total volume of the milling jar. After micro-nano-dispersion, a soluble polyarylene ether coating is obtained. After the base material is cleaned, the surface of the base material is dried and preheated, and then air is sprayed on the surface of the base material, and the coating is cured at high temperature to obtain a coating.

[0046] Example 5 Preparation of soluble polyarylene ether: Using a 250 mL polymerization reactor as an example, the following raw materials were prepared: twisted non-coplanar monomer 9,9'-bis(4-hydroxyphenyl)xanthene (20 mmol), 4,4-difluorobenzophenone (10 mmol), 2,6-difluorobenzonitrile (10 mmol), catalyst potassium carbonate (28 mmol), water-carrying agent toluene (40 mL), and reaction solvent sulfolane (30 mL). Nitrogen was then introduced into the reaction system, cooling water was passed through the condenser, and the temperature was slowly raised to 140°C for azeotropic dehydration. The reaction was then refluxed for 4 hours and then raised to 200°C. During this time, the water-carrying agent and water mixture was removed, and polymerization began. During this period, the viscosity of the polymerization system gradually increased. Based on the system's behavior, an appropriate amount of reaction solvent was added until the viscosity stopped rising. 40 mL of solvent was then added to dilute the mixture and rapidly stirred. The polymer mixture was slowly poured into a dilute acid solution, resulting in the precipitation of a white, fibrous polymer. The mixture was then washed repeatedly with ethanol and water to obtain the soluble polyarylene ether.

[0047] Preparation of dispersant: Taking a 250mL polymerization reactor as an example, prepare the raw materials according to the following mass: phenolphthalein (10mmol), hexafluorobisphenol A (10mmol), 4,4-difluorobenzophenone (20mmol), catalyst potassium carbonate (28mmol), water-carrying agent toluene (40mL), and cyclopentane sulfone (30mL). Then, nitrogen was introduced into the reaction system, cooling water was introduced into the condenser, and the temperature was slowly raised to 140°C for azeotropic dehydration. The mixture was refluxed for 4 hours, and then the temperature was raised to 200°C. During this period, the water-carrying agent and water mixture were discharged to start the polymerization reaction. During this period, the viscosity of the polymerization system will gradually increase. According to the system phenomenon, an appropriate amount of reaction solvent is added until the viscosity no longer increases. 40mL of solvent is added to dilute it and stir rapidly. The polymer mixture is slowly poured into a dilute acid solution to precipitate a fibrous polymer. After multiple cycles of washing with ethanol and water, a fluorine-containing polar polyaryletherketone, i.e., a dispersant, is obtained. The prepared dispersant was subjected to infrared detection, and the results are as follows Figure 1 As shown, after infrared detection at 1171cm -1 The absorption peak of -CF3 is 1649cm -1 The characteristic absorption peak of the carbonyl group of the ketone group is at 1716 cm -1 , indicating that the dispersant of the present invention has been prepared.

[0048] Preparation of a soluble polyarylene ether coating: Prepare raw materials, including 5 phr of soluble polyarylene ether, 10 phr of lubricant polytetrafluoroethylene, 67.7 phr of organic solvent N-methylpyrrolidone, 10 phr of the dispersant prepared above, 0.1 phr of anti-settling agent, 5 phr of defoamer, 0.1 phr of leveling agent, 2 phr of coupling agent, and 0.1 phr of pigment. The coating is micro-nano-milled using a planetary ball mill. The milling process is as follows: rotation speed of 100-3000 rpm, orbital speed of 50-2000 rpm, forward stirring for 30-60 minutes, reverse stirring for 30-60 minutes, and 2-4 cycles. The ratio of ball mill mass to total coating mass is 0.1-2, and the ball mill mass and material account for 0.5-0.9 of the total volume of the milling jar. After micro-nano-dispersion, a soluble polyarylene ether coating is obtained. After the base material is cleaned, the surface of the base material is dried and preheated, and then air is sprayed on the surface of the base material, and the coating is cured at high temperature to obtain a coating.

[0049] Comparative Example 1 The difference from Example 3 is that the dispersant is Efka PU 4063 AN (modified polyurethane, BASF).

[0050] Comparative Example 2 The difference from Example 3 is that the lubricant is molybdenum disulfide.

[0051] Comparative Example 3 The difference from Example 3 is that hexafluorobisphenol A is not used in the preparation of the dispersant.

[0052] Comparative Example 4 The difference from Example 3 is that 2,6-difluorobenzonitrile is not used in the preparation of the soluble polyarylene ether.

[0053] Comparative Example 5 The difference from Example 3 is that 4,4-difluorobenzophenone is not used in the preparation of the soluble polyarylene ether.

[0054] The soluble polyarylene ether coating films prepared in the Examples and Comparative Examples were tested by spraying the coatings onto iron plates. The following test items were tested: circle adhesion: tested according to the test method provided in GB / T 1720-2020; impact resistance: tested according to the test method provided in GB / T 1732-2020; flexibility: tested according to the test method provided in Article 4 of GB / T 1731-2020; pencil hardness: tested according to the test method provided in GB / T 6739-2022. The test results are shown in Table 1 below.

[0055] Table 1: Test results of paint film properties of soluble polyarylene ether coatings in Examples and Comparative Examples

[0056] In Examples 1-5, cyano functional groups were introduced to increase the polarity of the molecular chain, enhance adhesion, and improve the bonding strength between the coating and the metal. The dispersant prepared by the present invention was used to stably disperse the fluorinated lubricant in the soluble polyarylene ether coating, preventing lubricant agglomeration and improving the impact resistance, flexibility, and hardness of the soluble polyarylene ether coating film. In Comparative Example 1, a commonly used dispersant in the prior art was used, while in Comparative Example 2, other lubricants were used. In Comparative Example 3, hexafluorobisphenol A was not used in the preparation of the dispersant. The impact resistance, flexibility, and hardness of the resulting soluble polyarylene ether coating film were all reduced, indicating that the specific dispersant prepared by the present invention can stably disperse the fluorinated lubricant in the coating, further improving the coating's performance. In Comparative Example 4, 2,6-difluorobenzonitrile was not used, resulting in reduced adhesion of the coating film. In Comparative Example 5, 4,4-difluorobenzophenone was not used in the preparation of the soluble polyarylene ether, resulting in reduced adhesion and other properties of the coating film.

[0057] The above is a further detailed description of the present invention in conjunction with specific preferred embodiments, and the specific implementation of the present invention should not be considered to be limited to these descriptions. For those skilled in the art to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the scope of protection of the present invention.

Claims

1. A soluble polyarylether oily paint, characterized in that: The invention comprises the following raw materials in parts by weight: Soluble polyarylether 5-15phr, lubricant 3-10phr, organic solvent 50-80phr, dispersant 1-10phr, anti-settling agent 0.1-5phr, defoamer 0.1-5phr, leveling agent 0.1-3phr and coupling agent 0.1-2phr; The soluble polyarylether is prepared from a cyano-containing dihalogen monomer A, a dihalogen monomer B and a twisted non-coplanar monomer; the dispersant is prepared from phenolphthalein, 4,4'-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent; and the lubricant is a fluorine-containing lubricant.

2. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The twisted non-coplanar monomer is selected from one or more of 1,4-cyclohexanedimethanol, phenolphthalein, 3,3-(2,4-diamino-6,7-pterydine-diyl)diphenol, phenolphthalein, 1,5-naphthalenediol, 2,5-triptylidenediol, 9,9'-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-isopropyl-4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxy-1-naphthyl)phthalide, 9,9'-bis(4-hydroxyphenyl)xanthene, and 9,9'-bis(3-nitro-4-hydroxyphenyl)xanthene.

3. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The cyano-containing dihalogen monomer A is selected from 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile; the structural formula of the dihalogen monomer B is as follows: 。 4. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The ratio of the molar number of the twisted non-coplanar monomer to the total molar number of the cyano-containing dihalogen monomer A and the dihalogen monomer B in the soluble polyarylene ether is 1:1; the molar number of the cyano-containing dihalogen monomer A accounts for 10%-90% of the total molar number of the cyano-containing dihalogen monomer A and the dihalogen monomer B.

5. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The molar number of phenolphthalein in the dispersant accounts for 25%-75% of the total molar number of phenolphthalein and hexafluorobisphenol A; the ratio of the sum of the molar numbers of phenolphthalein and hexafluorobisphenol A monomers to the molar number of the catalyst is 1:(0.8-1.8).

6. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The catalyst is an alkali metal carbonate, and the water-carrying agent is selected from one or both of toluene and xylene.

7. The soluble polyarylether oil-based paint according to claim 1, characterized in that: The preparation method of the dispersant comprises the following steps: Phenolphthalein, 4,4'-difluorobenzophenone, hexafluorobisphenol A, a catalyst and a water-carrying agent are added to a reaction solvent. Under heating conditions, the water-carrying agent is used to carry out water, and then the water-carrying agent is removed and the heating is continued to carry out the reaction. As the viscosity of the reaction solution increases, the solvent is gradually added dropwise. When the viscosity of the system no longer increases, the solvent is added to adjust the mass fraction of the system to 30wt%, the temperature is lowered to stop the reaction, and the reaction solution is poured into a dilute acid solution to terminate the reaction to obtain a fibrous polymer, which is then treated to obtain the dispersant.

8. The soluble polyarylether oil-based paint according to claim 7, characterized in that: The temperature of the water is 130-160℃, and the time is 2-5h; the heating temperature is 180-210℃, and the time is 6-20h.

9. The soluble polyarylether oil-based paint according to claim 7, characterized in that: The treatment process includes: crushing the fibrous polymer, washing it thoroughly with water and ethanol, and then drying it.

10. Use of the soluble polyarylether oily paint according to any one of claims 1 to 9 on the surface of a metal substrate, characterized in that: The metal substrate is selected from one of iron plate, steel plate, aluminum plate or copper plate, and the coating method is spraying.

Images