CN-122013529-A - Water-based thermoplastic sizing agent doped with nano material, and preparation method and application thereof

CN122013529ACN 122013529 ACN122013529 ACN 122013529ACN-122013529-A

Abstract

The invention discloses a nano-material-doped aqueous thermoplastic sizing agent and a preparation method and application thereof, and belongs to the technical field of composite materials. The sizing agent takes bisphenol compound-diphenolic acid-dihalogenodiphenylketone/sulfone copolymer as matrix resin, and is synthesized into carboxyl-containing polyaryletherketone/sulfone copolymer through S N 2 nucleophilic polycondensation, and the carboxyl-containing polyaryletherketone/sulfone copolymer is prepared into an aqueous sizing agent by adopting an emulsion/solvent evaporation method, and is further doped with nano materials such as graphene oxide, multi-wall carbon nano tubes and the like. The sizing agent uses water as a dispersion medium, is environment-friendly, has excellent heat resistance and good compatibility with high-performance thermoplastic resins such as phenolphthalein polyether ketone, and can remarkably improve the interfacial bonding strength, interlaminar shear strength, bending strength and monofilament tensile strength of the carbon fiber composite material. The preparation process is simple and controllable, and is suitable for preparing the high-performance carbon fiber composite material in the fields of aerospace, mechano-electronics and the like.

Inventors

WANG HONGHUA
YU KEXIN
XIE GANG
ZHOU ZHENGWEI
ZHANG HONGYAN

Assignees

浙江理工大学
浙江精工集成科技股份有限公司

Dates

Publication Date: 20260512
Application Date: 20260410

Claims (10)

1. The aqueous thermoplastic sizing agent doped with the nano material is characterized by comprising the following components in percentage by mass: 0.5% -5% of matrix resin, 0.1 To 1 percent of nano material, 0.1% -2% Of surfactant, The balance of deionized water; The matrix resin is a carboxyl-containing polyaryletherketone/sulfone copolymer, and has a structure shown in a formula I: ; wherein X is selected from one of the following structures: ; y is selected from one of the following structures: 。
2. The aqueous thermoplastic sizing agent doped with nano materials according to claim 1, wherein the intrinsic viscosity of the carboxyl-containing polyaryletherketone/sulfone copolymer is 0.3-0.35 dL/g, the nano materials are selected from one or more of graphene oxide, hydroxylated multi-wall carbon nanotubes, carboxylated multi-wall carbon nanotubes, aminated multi-wall carbon nanotubes and nano silicon dioxide, and the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide and fatty alcohol polyoxyethylene ether.
3. A method for preparing the aqueous thermoplastic sizing agent according to any one of claims 1 to 2, comprising the steps of: S1, synthesizing matrix resin, namely dissolving bisphenol compound, diphenolic acid and dihalide compound in a polar aprotic solvent under the protection of inert atmosphere, adding a salifying agent and a water-carrying agent, sequentially carrying out water-carrying reaction and polymerization reaction, and acidizing, precipitating, washing and drying after the reaction is finished to obtain a carboxyl-containing polyaryletherketone/sulfone copolymer, wherein the dihalide compound has a structure shown in a formula II: ; wherein R is independently selected from fluorine or chlorine; S2, preparing a preliminary sizing agent, namely dissolving the matrix resin obtained in the step S1 in an organic solvent which is not mutually soluble with water to obtain an oil phase resin solution, dissolving a surfactant in deionized water to obtain an aqueous phase solution, dropwise adding the oil phase resin solution into the aqueous phase solution under stirring, and removing the organic solvent after emulsification treatment to obtain the preliminary aqueous sizing agent; s3, doping the nano material, namely adding the nano material into the preliminary aqueous sizing agent obtained in the step S2, and performing dispersion treatment to obtain the aqueous thermoplastic sizing agent doped with the nano material.
4. The preparation method of claim 3, wherein in the step S1, the bisphenol compound is selected from one or more of hydroquinone, biphenol, bisphenol A, phenolphthalein, bisphenol fluorene and N-phenylindolinone, the molar ratio of the bisphenol compound to the diphenolic acid is 1:0.1-1, the molar ratio of the bisphenol compound to the dihalide compound is 0.1-1:1, the salt former is potassium carbonate and/or sodium carbonate, and the molar ratio of the bisphenol compound to the salt former is 1:1-1.5.
5. The preparation method according to claim 3, wherein in the step S1, the polar aprotic solvent is selected from at least one of sulfolane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, the water-carrying agent is toluene and/or xylene, the water-carrying reaction temperature is 140-160 ℃ for 2-3 hours, the polymerization reaction temperature is 180-220 ℃ for 4-6 hours.
6. The preparation method of claim 3, wherein in the step S2, the water-immiscible organic solvent is selected from one of dichloromethane, chloroform and 1, 1-dichloroethane, and the emulsifying treatment is carried out by ultrasonic shearing for 15-30 min.
7. The method according to claim 3, wherein in the step S3, the dispersion treatment comprises ultrasonic dispersion for 15-30 min at 400-1000W, and stirring at 500-1500 rpm for 2-4 h.
8. Use of the aqueous thermoplastic sizing agent according to any of claims 1-2 for the preparation of carbon fiber reinforced thermoplastic composites, characterized in that it comprises the following steps: (1) Immersing the carbon fiber fabric into the sizing agent for sizing treatment, and then drying to obtain the sized carbon fiber fabric; (2) And alternately stacking the sized carbon fiber fabric and the thermoplastic resin film, and performing hot press molding to obtain the carbon fiber reinforced thermoplastic composite material.
9. The use according to claim 8, wherein in the step (1), the impregnation time of the sizing treatment is 1-2 hours, the drying temperature is 100-150 ℃, the drying time is 12-24 hours, and the sizing amount is controlled to be 1.0% -5.0% of the mass of the carbon fiber fabric.
10. The application of the thermoplastic resin film according to claim 8, wherein in the step (2), the thermoplastic resin film is a phenolphthalein polyether ketone film, and the hot press molding condition is that the temperature is 320-380 ℃, the pressure is 5-10 MPa, and the time is 30-60 min.

Description

Water-based thermoplastic sizing agent doped with nano material, and preparation method and application thereof Technical Field The invention belongs to the technical field of composite materials, and particularly relates to a nano-material-doped aqueous thermoplastic sizing agent, and a preparation method and application thereof. Background The carbon fiber reinforced thermoplastic resin matrix Composite (CFRTP) has wide application prospect in the high-tech fields of aerospace, national defense equipment, automobile industry, electronics and electrics and the like by virtue of excellent mechanical property, good processability, recoverability and rapid prototyping potential. Carbon fiber is used as a reinforcement body and has a series of advantages of high specific strength, high specific modulus, corrosion resistance and the like, but the surface of the carbon fiber is chemically inert and smooth, so that the interface bonding performance between the carbon fiber and a resin matrix is generally weak, and the carbon fiber becomes a key bottleneck for restricting the improvement of the overall performance of the composite material. In order to solve the interface problem, the sizing method is widely applied to carbon fiber production as an efficient and energy-saving surface treatment process. By coating a thin sizing agent on the surface of the fiber, the functions of protecting the fiber, reducing broken filaments and improving bundling property can be achieved, and more importantly, an effective interface transition layer can be constructed between the fiber and the resin, so that the stress transmission is optimized. However, most of carbon fiber sizing agents used in industry at present are thermosetting epoxy resin systems, and when the carbon fiber sizing agents are compounded with high-performance thermoplastic resins (such as PEEK, PEK, PES and the like), the problems of mismatching of chemical structures, insufficient heat-resistant temperature and the like exist, and degradation easily occurs in the high-temperature processing process generally required by the thermoplastic resins, so that the interface performance is damaged. In the prior art, development of thermoplastic sizing agents has been advanced, but there are still many limitations. For example, some techniques impart water solubility or improve adhesion to resins by introducing specific monomers or post-modifications, but often the synthesis steps are cumbersome, involve multiple acid-base adjustments and washes, have complex processes and are not conducive to large-scale production. Other technologies adopt a method of salinization of resin to realize water dispersion, but the residual organic solvent can not be completely avoided, and environmental protection and potential safety hazards exist. In addition, there have been attempts to introduce nanomaterials into sizing systems in an attempt to enhance the interface, but they have been concentrated in solvent-based systems or have failed to systematically address the problem of stable dispersion of nanomaterials in aqueous systems and synergistic interaction with the resin matrix. In summary, an aqueous thermoplastic sizing agent which has excellent heat resistance, good compatibility with high-performance thermoplastic resin, truly environmental friendliness and simple process is developed, and the nano reinforcing technology is effectively integrated, so that the method has important significance in breaking through the bottleneck of the interface performance of the carbon fiber/thermoplastic composite material and promoting wider application of the carbon fiber/thermoplastic composite material in the high-technology field. The present invention has been made in this context. Disclosure of Invention The invention provides a water-based high-temperature-resistant thermoplastic sizing agent doped with nano materials, and a preparation method and application thereof. The sizing agent is prepared by taking bio-based diphenolic acid as a key monomer, synthesizing carboxyl-containing polyaryletherketone/sulfone matrix resin through nucleophilic polycondensation, and dispersing the resin in water through emulsification and nano material (such as graphene oxide and functionalized carbon nano tube) doping. The product is environment-friendly, excellent in heat resistance, good in compatibility with high-performance resins such as PEK-C, capable of remarkably improving the interfacial bonding strength and comprehensive mechanical properties of the carbon fiber composite material, and suitable for the fields of aerospace and the like. In one aspect, the invention provides a nano-material-doped aqueous thermoplastic sizing agent, which adopts the following technical scheme: The nano-material doped aqueous thermoplastic sizing agent comprises the following components in percentage by mass: 0.5% -5% of matrix resin, 0.1 To 1 percent of nano material, 0.1% -2% Of surfactant, The balance of deio