Preparation method of bio-based polyaryletherketone emulsion

Abstract

The invention relates to bio-based polyaryletherketone synthesized by a one-step method, and belongs to the technical field of interface coatings, and the bio-based polyaryletherketone resin is used as a main slurry suitable for a sizing agent and the like and is used for preparing an emulsion. The emulsion is prepared from the following components in parts by weight: 0.5 to 3 parts of bio-based polyaryletherketone resin, 0.2 to 5 parts of an emulsifying agent, 0.1 to 1 part of a flatting agent, 0.1 to 1 part of a lubricating agent, 0.1 to 1 part of a de-foaming agent, 0.1 to 2 parts of an adhesive, 0.2 to 1 part of an antistatic agent and 86 to 98.7 parts of de-ionized water; according to the polyaryletherketone resin disclosed by the invention, the compatibility problem of an interface coating and polyaryletherketone matrix resin is effectively solved, the regularity of a polyaryletherketone molecular chain segment is reduced by introducing a benzene ring and acetal ring structure into a polymer molecular chain, and a space is reserved for contact between a solvent and the molecular chain, so that the polyaryletherketone resin has excellent solubility. Meanwhile, the interface adhesion can be enhanced through diffusion and physical entanglement effects between the sizing agent and matrix resin, it is guaranteed that the sizing agent and the polyaryletherketone matrix resin have excellent compatibility, and the sizing agent further has good thermal stability. Therefore, the interface bonding between the carbon fiber and the resin can be further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of interface coatings, and specifically relates to a method for preparing a bio-based polyaryletherketone emulsion, including but not limited to a method for preparing an emulsion using the bio-based polyaryletherketone synthesized by a one-step method and using the resin as a main slurry suitable for sizing agents, coatings, etc. Background Art

[0002] Carbon fiber is an inorganic fiber with a carbon main chain structure with a carbon content of more than 90% formed by the cracking and carbonization of organic fibers such as polyacrylonitrile (PAN) (or asphalt, viscose) under high temperature. Carbon fiber has excellent mechanical properties and chemical stability, lower density than aluminum and higher strength than steel. It is the fiber with the highest specific strength and specific modulus among the high-performance fibers currently produced in mass production. It has a series of excellent properties that cannot be replaced by other materials, such as light weight, high strength, high modulus, electrical conductivity, thermal conductivity, corrosion resistance, fatigue resistance, high temperature resistance, and small expansion coefficient. It is widely used in aerospace, wind turbine blades, sports and leisure, pressure vessels, carbon / carbon composite materials, transportation construction and other fields.

[0003] However, the smooth, non-polar surface of carbon fiber leads to poor bonding with the matrix resin and low mechanical properties. The surface modification of carbon fiber can improve the interfacial bonding strength between the fiber and the resin matrix, thereby improving the comprehensive mechanical properties of the composite material. The sizing method is not only simple to operate, but also can avoid contamination of the carbon fiber surface, protect the activity of the surface groups, improve the fiber bundling, and also can wet the carbon fiber, reduce the surface tension between the carbon fiber and the matrix resin, and enhance the interfacial bonding strength between the carbon fiber and the matrix resin, thereby improving the mechanical properties of the composite material. However, most of the commercial sizing agents today are thermosetting sizing agents, which are not compatible with thermoplastic resins. Polyetheretherketone is a thermoplastic resin whose repeating units are alternating ether bonds and ketone groups between benzene rings. It has the advantages of high strength, solvent resistance, and wide application. It also has polar groups, so the development of sizing agents suitable for polyetheretherketone has good application prospects.

[0004] Polyetheretherketone (PEEK) is an ideal choice for reinforcing composite materials because of its excellent mechanical properties, good thermal stability and chemical corrosion resistance. However, due to the chemical inertness of the PEEK surface, it is difficult for PEEK to fully infiltrate the surface of CFs, resulting in low bonding strength between CFs and PEEK, making the mechanical properties less than ideal. Therefore, according to the principle of "like dissolves like", polyaryletherketone with a structure similar to polyetheretherketone is selected as the main sizing resin of the sizing agent, and then modified to the carbon fiber surface by sizing to improve the interface performance between the carbon fiber and the matrix resin, so as to further improve the macroscopic performance of the composite material.

[0005] In recent years, some research has been conducted on sizing agents with polyaryletherketone resin as the main sizing agent, but the number is still small overall. Patent CN 102926204 A discloses an emulsion-type sizing agent for reinforcing CF / PEEK composite materials, but the main sizing agent of the sizing agent is epoxy resin, which is easy to decompose during processing. At the same time, there may be incompatibility between epoxy resin and the matrix resin PEEK, which limits its reinforcing effect. Patent CN 113563577 A discloses a phenolphthalein-modified polyaryletherketone water-based sizing agent, but the carboxyl content in the matrix resin of the sizing agent is not high, and the hydrophilicity is limited, which limits the mechanical properties of the reinforced composite material.

[0006] The advantages of polyaryletherketone are: (1) good performance. The rigid benzene ring in the molecular chain gives it strong hardness, and the flexible ether bond gives it good flexibility and impact resistance. In addition, the large conjugated structure formed between the benzene rings on the main chain makes it very stable. The bio-based polyaryletherketone high-performance emulsion prepared by the present invention is a high-solid coating with a solid content of 77% to 91%. Its advantages are: (1) It contains a small amount of organic volatile solvent, which saves solvent resources. It is an environmentally friendly emulsion that meets the national environmental protection requirements and future development trends. Easy construction. At present, there are few studies on sizing agents for carbon fibers of polyarylether resins. Therefore, it is of great research significance to develop a sizing agent for carbon fibers that matches the polyetheretherketone matrix resin. Summary of the invention

[0007] Compared with the prior art, the beneficial effects of the present invention include at least one of the following:

[0008] In the first aspect, the present invention provides a method for treating the surface of carbon fiber with an emulsion of a sizing agent, a coating, etc., which can improve the interfacial bonding strength between the carbon fiber and the polyetheretherketone resin, thereby improving the mechanical properties of the composite material. The preparation method thereof comprises the following steps:

[0009] (1) placing the bio-based polyaryletherketone resin in one or more solvents and stirring the resin sufficiently to completely dissolve the resin and form a uniform solution;

[0010] (2) adding an emulsifier to deionized water and stirring the mixture thoroughly, then adding the solution in step (1) thereto, mixing the mixture uniformly, and treating the mixture using a high-speed shear emulsifier while maintaining the solution temperature at 15 to 45° C. to obtain a mixed solution;

[0011] (3) adding a leveling agent, a lubricant, a defoaming agent, an adhesive and an antistatic agent to the mixed solution of step (2), stirring evenly, and then recovering the organic solvent by distillation or rotary evaporation to obtain a polyaryletherketone emulsion sizing agent;

[0012] The organic solvent described in step (1) includes but is not limited to one or more of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dichloromethane, chloroform, dioxane, ethyl acetate, perchloroethylene, and trichloroethylene.

[0013] The ultrasonic shearing treatment time in step (2) is 10 to 40 minutes, and the power is 100 to 1000 W;

[0014] In terms of mass percentage, the composition is: Bio-based polyaryletherketone resin 0.5-3%, emulsifier 0.2-5%, leveling agent 0.1-1%, lubricant 0.1-1%, defoamer 0.1-1%, adhesive 0.1-2%, antistatic agent 0.2-1%, deionized water 86-98.7%;

[0015] The structural formula of the polyaryletherketone resin in step (1) is shown in Formula 1:

[0016] 2. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that the bio-based polyaryletherketone resin is prepared in the following steps:

[0017] (1) Add the reactants bisphenol monomer, difluoro monomer, catalyst, toluene and sulfolane into a three-necked flask, stir mechanically under a nitrogen atmosphere, heat to 130-150° C., and then add water for 2-5 hours;

[0018] (2) After the water is removed, the toluene is discharged, the temperature is raised to 160-180°C and the reaction is carried out for 2-30 hours. When the product becomes viscous, it is poured into deionized water or water: anhydrous ethanol (50:50) to obtain a solid polymer;

[0019] (3) crushing the polymer with a small pulverizer, washing with deionized water, methanol, ethanol or a mixture of the three solutions in different proportions, and drying to obtain a bio-based polyaryletherketone polymer; The synthetic method of the bisphenol monomer is: Erythritol (5 g, 40 mmol) and vanillin (12.17 g, 80 mmol) were reacted in 33 mL of a mixed solvent (DMF: petroleum ether = 1:2) at 100 ° C under the catalysis of p-TSA·H2O (0.34 g, 2 wt% of the total mass of vanillin and erythritol) for 30 h. Subsequently, the mixture was concentrated and the petroleum ether was removed, and the crude product was poured into 100 mL of deionized water to precipitate the product, which was further filtered and washed three times with ethanol (10 mL). The vanillin derivative (VD) compound was obtained by drying in an oven at 80 ° C for 6 h.

[0020] (4) Catalyst: one or more of sodium carbonate, potassium carbonate, calcium oxide, and calcium hydroxide

[0021] (5) The structural formula of the difluoro monomer is one of (1) to (4)

[0022] Furthermore, the bio-based polyaryletherketone resin described in step (1) is prepared by the following method steps:

[0023] The reactants, a bisphenol monomer A, a difluoro monomer and a catalyst, are mixed in a mass ratio of (3-50:2-50):19-25:15-20, and then toluene and cyclopentane are added, and mechanical stirring is performed under a nitrogen atmosphere. The temperature is raised to 130-150° C. and then the reaction is performed for 2-6 hours to fully remove the water generated in the reaction. After the water is removed, the temperature is raised to 160-170° C. to evaporate the toluene, and then the temperature is raised to 160-180° C. to react for 2-30 hours to obtain a viscous solution, and then the viscous solution is poured into a mixed precipitant prepared in different proportions of deionized water and dilute hydrochloric acid, methanol or ethanol to precipitate a large amount of white polymer solids, and the polymer solids are crushed into fine powder by a pulverizer, and then repeatedly boiled and washed in a mixed solvent of deionized water with dilute hydrochloric acid, methanol or ethanol for 5-10 hours, and then dried at 60-120° C. to obtain a bio-based polyaryletherketone resin.

[0024] Furthermore, the emulsifier described in step (2) is one or any combination of hexadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, calcium stearate, benzyl chloride, laurel oil, palm oil, glutamic acid, glycine, α-alkyl betaine, N-alkyl betaine, fatty acid glyceride, Span 20, Span 60, Span 65, Span 80, Tween 20, Tween 40, Tween 80 or OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40, OP-50.

[0025] Furthermore, the leveling agent in step (3) is one or any combination of polyether-modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester-modified organic siloxane or alkyl-modified organic siloxane.

[0026] Furthermore, the lubricant described in step (3) is one or any combination of calcium stearate, stearic acid amide, N,N-ethylenebisstearamide, oleic acid amide, erucic acid amide, n-butyl stearate or glyceryl trihydroxystearate.

[0027] Furthermore, the defoaming agent in step (3) is one or any combination of polysiloxane, polyether-modified silicone oil, lauric acid, trialkyl melamine palmitate, melamine cyanurate chloride or fatty amine.

[0028] Furthermore, the adhesive in step (3) is one or any combination of starch, dextrin, polyvinyl alcohol, carboxymethyl cellulose, acrylate or ethyl acetate.

[0029] Furthermore, the antistatic agent described in step (3) is one or any combination of sodium dodecyl sulfate, ethoxylated lauric acid amine, glycerol monostearate, ethoxylated alkylamine or ethoxylated alkyl acid amine.

[0030] The present invention also provides an application of a bio-based polyaryletherketone emulsion in the field of preparing a carbon fiber reinforced polyaryletherketone composite material, and the method steps are as follows:

[0031] The commercial desized carbon fiber fabric is immersed in a bio-based polyaryletherketone emulsion for 8 to 60 seconds to obtain a carbon fiber fabric treated with the bio-based polyaryletherketone emulsion, and then dried at a drying temperature of 90 to 110°C. The dried carbon fiber fabric treated with the bio-based polyaryletherketone emulsion sizing is composited with a polyaryletherketone film, and then cut into an appropriate size and placed in a mold coated with a release agent. The fiber is hot-pressed with a laying direction of 180° to obtain a carbon fiber reinforced polyaryletherketone composite material.

[0032] Furthermore, the polyaryletherketone is any one of polyetheretherketone, polyetheretherketoneketone, polyetherketoneketone, polyetherketone or polyetherketoneetherketoneketone.

[0033] Beneficial effects of the present invention:

[0034] The present invention provides an emulsion of polyaryletherketone, wherein the main sizing agent is a resin composed of non-coplanar acetal groups. The introduction of acetal groups can destroy the regularity of the molecular chain of polyaryletherketone, improve the solubility of polyaryletherketone, and thus a sizing agent, adhesive or coating can be prepared through further processing. The sizing agent exhibits good kinetic stability, can be stored for 6 months or more without precipitation, and firmly adheres to the CF surface through π-π interaction and van der Waals force. At the same time, the good compatibility of the sizing agent with the PEEK matrix resin and the physical entanglement and diffusion between the molecular chains also bring about good interfacial bonding, enhance the bonding force between the matrix and the CF, and improve the interfacial adhesion.

[0035] The method adopted by the invention is simple, easy to operate, easy to implement repeatedly, environmentally friendly, low in cost, and has good industrialization prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0037] Figure 1 , Figure 2 The thermogravimetric curves and glass transition temperature curves of Example 2 and Example 3 of the present invention are respectively;

[0038] Figure 3 a. Figure 3 b. Figure 3 c and Figure 3 d are scanning electron microscope images of the original carbon fiber after removing the commercial sizing agent, and the carbon fiber coated with sizing agents of different concentrations in Example 1 of the present invention;

[0039] Figure 4 The particle sizes of the sizing agent at different concentrations obtained in Example 2 of the present invention are as follows;

[0040] Figure 5 This is a physical picture of the sizing agent obtained in Example 2 of the present invention after being stored for 6 months;

[0041] Figure 6 This is the test result of the interlaminar shear strength of the composite material in Example 3 of the present invention. DETAILED DESCRIPTION

[0042] The present invention is further described in detail below in conjunction with embodiment. Embodiment is only used to illustrate the present invention but is not intended to limit the scope of the present invention. After reading the content of the present invention, various changes or modifications made to the present invention by those skilled in the art, these equivalent forms also belong to the protection scope of the present invention.

[0043] Example 1

[0044] (1) Preparation of bio-based polyaryletherketone emulsion sizing agent:

[0045] Under nitrogen atmosphere, 7.83g bisphenol monomer, 4.56g 4,4'-difluorobenzophenone, 3.32g catalyst (mixture of anhydrous sodium carbonate and anhydrous potassium carbonate), 7mL toluene and 15mL sulfolane were mixed and stirred, and then heated to 135°C for 4h, toluene was evaporated, and then heated to 160°C for 5h, and then the mixture was poured into a mixed solvent of deionized water and methanol to obtain a white polymer solid. The polymer solid was crushed into fine powder by a pulverizer, and then repeatedly boiled and washed with a mixed solvent of deionized water and methanol for 7h, and then dried in a vacuum oven at 120°C to obtain a bio-based polyaryletherketone. The specific structural formula is as follows:

[0046]

[0047] (2) dissolving 2.6 g of the bio-based polyaryletherketone obtained in step (1) in dichloromethane to obtain a uniform solution;

[0048] (3) adding 0.7 g of hexadecyltrimethylammonium bromide to 150 mL of deionized water and 20 mL of dichloromethane solvent, stirring thoroughly, adding the solution obtained in step (2) and mixing evenly, and then subjecting the mixed solution to ultrasonic shearing for 10 min at a power of 450 W and maintaining the solution temperature at 20° C.;

[0049] (4) Add 2 g of polydimethylsiloxane, 4.5 g of calcium stearate, 2.5 g of polysiloxane, 6 g of carboxymethyl cellulose and 5.5 g of polymethyl acrylate to the mixed solution obtained in step (3), stir evenly, and then recover the organic solvent by distillation evaporation to obtain a bio-based polyaryletherketone emulsion sizing agent.

[0050] Preparation of carbon fiber reinforced polyetheretherketone (CF / PEEK) composites:

[0051] The commercial desized carbon fiber fabric is immersed in the emulsion sizing agent prepared in step (4) of Example 1 for 20 seconds to obtain carbon fiber modified with a bio-resistant polyaryletherketone sizing agent. The carbon fiber fabric is dried at 80°C and cut into fabrics of 12 cm×8 cm in size. The carbon fiber fabric is then compounded with polyetheretherketone powder and placed in a mold coated with a release agent. The fiber is laid in a 180° direction for hot pressing to obtain a carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material.

[0052] By changing the mass of the resin added into the organic solvent dichloromethane, emulsion sizing agents with concentrations of 0.5%, 1.5% and 2% were prepared respectively.

[0053] The carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material was tested, and the interlaminar shear strength of the carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material was measured to be 63.2-84.6MPa. Figure 6 shown.

[0054] Attached Figure 3 a is the commercial desizing carbon fiber and attached material used in Example 1 of the present invention. Figure 3 b. Figure 3 c. Figure 3 d and Figure 3 e is a comparison of scanning electron microscope images of carbon fibers treated with different concentrations of bio-based polyaryletherketone emulsion sizing agents. It can be seen that after the carbon fiber surface is coated with the polyaryletherketone emulsion sizing agent, a uniform PAEK resin film is attached to the carbon fiber surface and the grooves on the carbon fiber surface become shallower. The shallower surface grooves make up for the surface defects of the carbon fiber caused by wet spinning during the spinning process.

[0055] Table 1 shows the contact angle and surface energy data of the commercial desizing carbon fiber obtained in Example 1 of the present invention and the carbon fiber modified with a bio-based polyaryletherketone emulsion sizing agent. It can be concluded that after the bio-based polyaryletherketone emulsion sizing agent is coated on the surface of the carbon fiber, the wetting performance of the carbon fiber is significantly improved.

[0056]

[0057] Example 2

[0058] (1) Preparation of bio-based polyaryletherketone emulsion sizing agent:

[0059] Under a nitrogen atmosphere, 15.4 g of bisphenol monomer, 21.8 g of 4,4'-difluorobenzophenone, 17.8 g of catalyst (a mixture of anhydrous sodium carbonate and anhydrous potassium carbonate), 12 mL of toluene and 45 mL of N-methylpyrrolidone were mixed and stirred, and then the temperature was raised to 125°C for reaction for 4 hours, and then the toluene was evaporated. The mixture was then heated to 165°C for reaction for 6 hours, and then poured into a mixed solvent of deionized water and methanol to obtain a white polymer solid. The polymer solid was crushed into fine powder by a pulverizer, and then repeatedly boiled and washed with a mixed solvent of deionized water and methanol for 10 hours, and then dried in a vacuum oven at 120°C to obtain a bio-based polyaryletherketone.

[0060] (2) dissolving 13 g of the bio-based modified polyaryletherketone obtained in step (1) in tetrahydrofuran and dichloromethane to obtain a uniform solution;

[0061] (3) adding 15 g of sodium dodecylbenzene sulfonate to 960 mL of deionized water, stirring thoroughly, adding the solution obtained in step (2) and mixing evenly, and then subjecting the mixed solution to ultrasonic shearing for 5 min at a power of 600 W, and maintaining the solution temperature at 25 ° C.;

[0062] (4) Add 3 g of polyether-modified polysiloxane, 6 g of stearic acid amide, 3 g of polyether-modified silicone oil, 6 g of polyvinyl alcohol and 5 g of sodium dodecyl sulfate to the mixed solution obtained in step (3), stir evenly, and then recover the organic solvent by distillation evaporation to obtain a bio-based polyaryletherketone emulsion sizing agent.

[0063] Preparation of carbon fiber reinforced polyetheretherketone (CF / PEEK) composites:

[0064] The commercial desized carbon fiber fabric was immersed in the emulsion sizing agent prepared in step (4) of Example 1 for 15 seconds to obtain carbon fiber modified with a bio-resistant polyaryletherketone sizing agent. The carbon fiber was dried at 85°C and cut into fabrics of 12 cm×8 cm in size. The carbon fiber fabric was then compounded with polyetheretherketone powder and placed in a mold coated with a release agent. The fiber was laid in a 180° direction for hot pressing to obtain a carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material.

[0065] Figure 5 and Figure 4 The particle size diagram of the bio-based polyaryletherketone sizing agent emulsion of different concentrations prepared in Example 2 of the present invention and the particle size after storage for 6 months. The particle size of the bio-based polyaryletherketone sizing agent of different concentrations obtained in step (4) of Example 2 is 72-84nm. Figure 4 The obtained carbon fiber reinforced polyether ketone ketone (CF / PEEK) composite material was tested, and the measured interlaminar shear strength of the carbon fiber reinforced polyether ether ketone (CF / PEEK) composite material was 72.6MPa. Figure 6 shown.

[0066] Example 3

[0067] (1) Preparation of bio-based polyaryletherketone emulsion sizing agent:

[0068] In a nitrogen atmosphere, 11.75g ​​of bisphenol monomer, 18.8g of 4,4'-difluorobenzophenone, 13.5g of anhydrous potassium carbonate, 100mL of toluene and 150mL of dimethyl sulfoxide were mixed and stirred, and then heated to 138°C for 2.5h, toluene was evaporated, and then heated to 170°C for 3h, and then the mixture was poured into a mixed solvent of deionized water and ethanol to obtain a white polymer solid. After the polymer solid was crushed into fine powder by a pulverizer, it was repeatedly boiled and washed with a mixed solvent of deionized water and dilute hydrochloric acid for 20h, and then dried in a vacuum oven at 90°C to obtain a bio-based polyaryletherketone. The specific reaction formula is as follows:

[0069] (2) dissolving 17 g of the bio-based polyaryletherketone obtained in step (1) in dichloromethane to obtain a uniform solution;

[0070] (3) adding 10 g of stearic acid to 966 mL of deionized water, stirring thoroughly, then adding the solution obtained in step (2) and mixing evenly, and then subjecting the mixed solution to ultrasonic shearing for 12 min at a power of 500 W, and maintaining the solution temperature at 35 ° C.;

[0071] (4) Add 2 g of alkyl-modified organosiloxane, 5.5 g of oleic acid amide, 3 g of lauric acid, 7 g of dextrin and 5 g of ethoxylauric acid amide to the mixed solution obtained in step (3), stir evenly, and then use rotary evaporation to recover the organic solvent to obtain a bio-based polyaryletherketone emulsion sizing agent.

[0072] Preparation of carbon fiber reinforced polyetheretherketone (CF / PEEK) composites:

[0073] The commercial desized carbon fiber fabric is immersed in the emulsion sizing agent prepared in step (4) of Example 1 for 25 seconds to obtain carbon fiber modified with a bio-resistant polyaryletherketone sizing agent. The carbon fiber fabric is dried at 90°C and cut into fabrics of 12 cm×8 cm in size. The carbon fiber fabric is then compounded with polyetheretherketone powder and placed in a mold coated with a release agent. The fiber is laid in a 180° direction for hot pressing to obtain a carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material.

[0074] Attached Figure 1 , attached Figure 2 They are the thermogravimetric curves and glass transition temperature diagrams of the bio-based polyaryletherketone obtained in Examples 2 and 3 of the present invention, respectively. It can be seen that the thermogravimetric temperatures of the bio-based polyaryletherketone when the mass loss is 5% are 360 ​​and 390°C and the glass transition temperatures are 137 and 152°C, which can prove the high temperature resistance of this resin.

[0075] Attached Figure 6 The unmodified carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material and the carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material modified with different concentrations of bio-based polyaryletherketone sizing agent emulsion prepared in Example 3 of the present invention were tested. The interlaminar shear strength of the carbon fiber reinforced polyetheretherketone (CF / PEEK) composite material was 60-80MPa. This result shows that the composite materials modified with the emulsion sizing agent have different degrees of improvement in mechanical properties.

[0076] It should be understood that the application of the present invention is not limited to the above examples, and the design concept of the present invention is not limited thereto. Any non-substantial changes to the present invention using this concept should fall within the scope of protection of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments in any form based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. The preparation method of the bio-based polyaryletherketone emulsion sizing agent comprises the following steps: (1) placing the bio-based polyaryletherketone resin in one or more solvents and stirring the resin sufficiently to completely dissolve the resin and form a uniform solution; (2) adding the emulsifier into deionized water and stirring thoroughly, and then adding the solution in step (1) thereto, The mixture is mixed evenly, treated with a high-speed shear emulsifier, and the solution temperature is maintained at 15 to 45° C. to obtain a mixed solution; (3) adding a leveling agent, a lubricant, a defoaming agent, an adhesive and an antistatic agent to the mixed solution of step (2), stirring evenly, and then recovering the organic solvent by distillation or rotary evaporation to obtain a polyaryletherketone emulsion sizing agent; The organic solvent described in step (1) includes but is not limited to one or more of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dichloromethane, chloroform, dioxane, ethyl acetate, perchloroethylene, and trichloroethylene. The ultrasonic shearing treatment time in step (2) is 10 to 40 minutes, and the power is 100 to 1000 W; In terms of mass percentage, the composition is: Bio-based polyaryletherketone resin 0.5-3%, emulsifier 0.2-5%, leveling agent 0.1-1%, lubricant 0.1-1%, defoamer 0.1-1%, adhesive 0.1-2%, antistatic agent 0.2-1%, deionized water 86-98.7%; The structural formula of the bio-based polyaryletherketone resin in step (1) is shown in Formula 1:

2. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The bio-based polyaryletherketone resin is prepared in the following steps: (1) Add the reactants bisphenol monomer, difluoro monomer, catalyst, toluene and sulfolane into a three-necked flask, stir mechanically under a nitrogen atmosphere, heat to 130-150° C., and then add water for 2-5 hours; (2) After the water is removed, the toluene is discharged, the temperature is raised to 160-180°C and the reaction is carried out for 2-30 hours. When the product becomes viscous, it is poured into deionized water or water: anhydrous ethanol (50:50) to obtain a solid polymer; (3) crushing the polymer with a small pulverizer, washing with deionized water, methanol, ethanol or a mixture of the three solutions in different proportions, and drying to obtain a bio-based polyaryletherketone polymer; The synthesis steps of the reactive bisphenol monomer are as follows: Erythritol (5 g, 40 mmol) and vanillin (12.17 g, 80 mmol) were reacted in 33 mL of a mixed solvent (DMF: petroleum ether = 1:2) at 100 ° C under the catalysis of p-TSA·H2O (0.34 g, 2 wt% of the total mass of vanillin and erythritol) for 30 h. Subsequently, the mixture was concentrated and the petroleum ether was removed, and the crude product was poured into 100 mL of deionized water to precipitate the product, which was further filtered and washed three times with ethanol (10 mL). The vanillin derivative (VD) compound was obtained by drying in an oven at 80 ° C for 6 h. (4) Catalyst: one or more of sodium carbonate, potassium carbonate, calcium oxide, and calcium hydroxide (5) The structural formula of the difluoro monomer is one of (1) to (4) 3. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The emulsifier is one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfonate, sodium dodecyl sulfate, benzalkonium chloride, Tween series, polyoxyethylene monooleate, polyoxyethylene monolaurate, sodium oleate, potassium oleate, OP series or castor oil polyoxyethylene ether series.

4. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The leveling agent is one or more of hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, acrylic resin, urea-formaldehyde resin, polyvinyl pyrrolidone, polyurethane or melamine formaldehyde resin.

5. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The lubricant is one or more of polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.

6. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The adhesive is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, sodium polyacrylate, acrylates, ethyl acetates, and polyvinyl alcohols.

7. A bio-based polyaryletherketone sizing agent according to claim 1, characterized in that: The antistatic agent is one or more of polyethylene glycol methacrylic acid copolymer, polyether ester amide, polyether ester acetamide, polyethylene oxide, propylene oxide copolymer or polyethylene glycol bismaleic acid monoester.

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