阅读说明：本技术 碳纤维用复合型耐高温上浆剂、其制备方法及应用 (Composite high-temperature-resistant sizing agent for carbon fibers, and preparation method and application thereof ) 是由 郭强 吴兆辉 曹志强 刘海彬 杨健伟 何翔 汪恒 毕宸洋 于 2020-12-10 设计创作，主要内容包括：本发明涉及一种用于制备聚醚醚酮、聚苯硫醚、聚苯硫醚砜、聚醚砜、聚酰亚胺、聚醚酰亚胺或聚四氟乙烯为基体复合材料及3D打印料的增强碳纤维表面上浆用复合型耐高温上浆剂及应用方法：包括耐高温上浆剂的制备方法、商品碳纤维的褪浆工艺、对褪浆商品碳纤维再上浆耐高温上浆剂的工艺,以及复合材料及3D打印料的制备工艺参数设定。该耐高温上浆剂的组成及质量百分比为：0.2～10wt％的聚苯硫醚砜,0.1～5wt％的聚醚砜,0.1～5wt％聚醚酰亚胺,80～99.6wt％的有机溶剂。本发明为用以填充增强加工温度在330～380℃范围的耐高温基体树脂的碳纤维提供一种耐高温上浆剂,可以明显改善碳纤维与树脂基体之间的界面作用,提高复合材料及3D打印料的力学性能。(The invention relates to a composite high-temperature-resistant sizing agent for sizing the surface of reinforced carbon fibers for preparing a composite material taking polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyetherimide or polytetrafluoroethylene as a matrix and a 3D printing material and an application method thereof, wherein the composite high-temperature-resistant sizing agent comprises the following components in parts by weight: the preparation method comprises a preparation method of the high-temperature-resistant sizing agent, a desizing process of the commercial carbon fiber, a process of repulping the high-temperature-resistant sizing agent to the desized commercial carbon fiber, and preparation process parameter setting of the composite material and the 3D printing material. The high-temperature resistant sizing agent comprises the following components in percentage by mass: 0.2-10 wt% of polyphenylene sulfide sulfone, 0.1-5 wt% of polyether sulfone, 0.1-5 wt% of polyetherimide and 80-99.6 wt% of organic solvent. The high-temperature-resistant sizing agent is provided for the carbon fibers filled with the high-temperature-resistant matrix resin with the reinforced processing temperature of 330-380 ℃, so that the interface effect between the carbon fibers and the resin matrix can be obviously improved, and the mechanical properties of the composite material and the 3D printing material are improved.)

1. A composite high-temperature-resistant sizing agent for carbon fibers is characterized in that: is a solution type material, and comprises the following components in percentage by mass: 0.2-10 wt% of polyphenylene sulfide sulfone, 0.1-5 wt% of polyether sulfone, 0.1-5 wt% of polyetherimide and 80-99.6 wt% of organic solvent, wherein the organic solvent is N-ethyl pyrrolidone, N-dimethylacetamide or sulfolane; the composite high-temperature-resistant sizing agent for the carbon fibers is used for preparing a composite material with polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyether imide or polytetrafluoroethylene as a matrix or a composite high-temperature-resistant sizing agent for sizing the surface of reinforced carbon fibers of a 3D printing material.

2. A method for preparing the composite type high temperature resistant sizing agent for carbon fibers according to claim 1, comprising the steps of:

at 40-60 ℃, dissolving polyphenylene sulfide sulfone in an organic solvent, and mechanically stirring for 5-10 min;

and then respectively adding polyether sulfone and polyetherimide, and mechanically stirring for 10-20 min to form a uniform solution, thereby obtaining the composite high-temperature-resistant sizing agent.

3. A process for desizing and then sizing commercial carbon fibers, which utilizes the composite high-temperature-resistant sizing agent for the carbon fibers as claimed in claim 1 to carry out repulping modification treatment on the commercial carbon fibers which are desized cleanly in advance, and is characterized by comprising the following steps of:

a. adopting de-sizing liquid to carry out de-sizing treatment on the original sizing agent on the surface of the carbon fiber to be treated, wherein the carbon fiber to be treated is a commercial carbon fiber which is sized with a universal sizing agent; placing the carbon fiber in an environment of 110-180 ℃ for 1-5 min, taking out, quickly placing the carbon fiber into liquid nitrogen for soaking for 5-60 s, taking out, placing the carbon fiber into de-starching liquid, ultrasonically oscillating for 15-120 min, taking out, and drying to obtain the de-starched carbon fiber;

b. the re-sizing process of carbon fiber is completed by re-sizing the surface of the carbon fiber that has been degummed clean with the composite high temperature resistant sizing agent for carbon fiber according to claim 1.

4. The carbon fiber repulping process method according to claim 3, wherein in the step a, the desizing liquid comprises the following components in percentage by mass: 20-40 wt% of dichloromethane, 20-40 wt% of benzyl alcohol, 10-30 wt% of methanol, 5-10 wt% of N-ethyl pyrrolidone, 0.5-3 wt% of phenol, 2-7 wt% of hydrogen peroxide and 2.5-10 wt% of cetyl trimethyl ammonium bromide serving as a surfactant.

5. The carbon fiber re-sizing process method according to claim 3, wherein in the step b, the carbon fibers are preheated to 40-60 ℃ by the composite high-temperature-resistant sizing agent, the carbon fibers which are completely degummed are placed into the composite high-temperature-resistant sizing agent for carbon fibers to be soaked for 5-30 s, the carbon fibers are taken out to be scraped off to remove redundant sizing agent, and the carbon fibers are dried for 10-60 min at 60-100 ℃ to obtain the carbon fibers which are re-sized by the composite high-temperature-resistant sizing agent.

6. A high temperature resistant matrix resin composite or 3D printing material, characterized in that: polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyether imide or polytetrafluoroethylene high-temperature-resistant resin is taken as a matrix; re-sizing the composite high-temperature-resistant sizing agent prepared by the carbon fiber re-sizing process method according to claim 3 with carbon fiber and high-temperature-resistant matrix resin for extrusion granulation, or cutting into short fibers filled with the high-temperature-resistant matrix resin, wherein the filling amount of the carbon fibers is 15-50 wt%, and performing hot forming at 330-380 ℃ to obtain the carbon fiber reinforced high-temperature-resistant matrix resin composite material or a 3D printing material product.

Technical Field

The invention relates to a preparation method of a composite high-temperature-resistant sizing agent for sizing the surface of reinforced carbon fibers, and process parameter setting of the composite high-temperature-resistant sizing agent for preparing polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyether imide or polytetrafluoroethylene matrix composite materials and 3D printing materials by re-sizing commercial carbon fibers.

Background

Carbon fiber is a high-strength light inorganic carbon material, is commonly used for reinforcing organic polymer resin to prepare composite materials, can obviously improve the strength of polymer resin, and is widely applied to the fields of aviation, aerospace, national defense equipment, mechanical equipment and the like. Before leaving a factory, the commercial carbon fiber is generally subjected to sizing treatment by adopting a universal sizing agent, and the function of the sizing agent is as follows:

firstly, carbon fibers are bundled, so that friction among the carbon fibers is reduced, and the surfaces of the carbon fibers are protected;

and secondly, a polymer layer is formed on the surface of the carbon fiber through sizing treatment to play a role of a coupling agent, so that the chemical combination between the carbon fiber and the resin is improved, and the interface performance of the composite material is improved. Currently, commercial carbon fibers mostly adopt a general epoxy resin sizing agent, and a small part of the commercial carbon fibers adopt sizing agents such as phenolic resin, polyurethane and the like.

When commercial carbon fibers are used for reinforcing general plastics such as polypropylene and polyethylene, or engineering plastics such as polyamide and polycarbonate, the reinforcing effect is generally remarkable. However, when the commercial carbon fibers are used for reinforcing high temperature resistant matrix resins such as polyetheretherketone, polyphenylene sulfide sulfone, polyethersulfone, polyimide, polyetherimide or polytetrafluoroethylene, since the processing temperature of the commercial carbon fibers is generally as high as 330 ℃ or higher, the general epoxy resin sizing agent on the surface of the commercial carbon fibers is gradually degraded and loses effect at the high temperature, and the bonding between the carbon fibers and the matrix resin may be seriously damaged, so that the reinforcing effect of the commercial carbon fibers on the high temperature resistant matrix resin is not good. The composite high-temperature-resistant sizing agent can be used for effectively solving the problems, but due to the relation between the requirement and the cost, the composite high-temperature-resistant sizing agent is rarely directly used for commercial carbon fibers when the carbon fibers leave a factory. Purchasing commodity carbon fibers, then removing the original sizing agents such as epoxy resin and the like, and re-sizing the composite high-temperature-resistant sizing agent to modify the high-temperature-resistant matrix resin is an economical and feasible solution, but no relevant report is found yet.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a composite high-temperature-resistant sizing agent for carbon fibers, which comprises a preparation method and application thereof, is suitable for processing technologies of high-temperature-resistant matrix resins such as polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyetherimide or polytetrafluoroethylene, and the like, desizing and re-sizing modification treatment are carried out on commercial carbon fibers, so that the composite high-temperature-resistant sizing agent is an effective way for improving the interface bonding force between the carbon fibers and the resins such as the polyether-ether-ketone and improving various properties of composite materials, and can effectively promote the application of the carbon fibers in the high-temperature-resistant matrix resins.

In order to achieve the purpose of the invention, the invention adopts the following technical scheme:

one of the purposes of the invention is to provide a composite high-temperature-resistant sizing agent for carbon fibers, which is a solution type material and comprises the following components in percentage by mass: 0.2-10 wt% of polyphenylene sulfide sulfone, 0.1-5 wt% of polyether sulfone, 0.1-5 wt% of polyetherimide and 80-99.6 wt% of organic solvent, wherein the organic solvent is N-ethyl pyrrolidone, N-dimethylacetamide or sulfolane; the composite high-temperature-resistant sizing agent for the carbon fibers is used for preparing a composite material with polyether-ether-ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyether imide or polytetrafluoroethylene as a matrix or a composite high-temperature-resistant sizing agent for sizing the surface of reinforced carbon fibers of a 3D printing material.

A preparation method of a composite high-temperature-resistant sizing agent for carbon fibers comprises the following steps:

at 40-60 ℃, dissolving polyphenylene sulfide sulfone in an organic solvent, and mechanically stirring for 5-10 min; and then respectively adding polyether sulfone and polyetherimide, and mechanically stirring for 10-20 min to form a uniform solution, thereby obtaining the composite high-temperature-resistant sizing agent.

The composite high-temperature-resistant sizing agent consists of high-temperature-resistant resin and an organic solvent. Wherein the high temperature resistant resin comprises polyphenylene sulfide sulfone, polyether sulfone and polyether imide. The polyphenylene sulfide sulfone used as the main material of the sizing agent has outstanding high temperature resistance and mechanical property, the compatibility of polyether sulfone, polyether imide, polyether ether ketone and other high temperature resistant matrix resins is better, and the three materials are jointly used as the sizing agent, which is favorable for further improving the interface strength of carbon fibers and the high temperature resistant matrix resins.

The invention discloses a process method for desizing and then sizing commercial carbon fibers, which utilizes a composite high-temperature-resistant sizing agent for the carbon fibers to perform repulping modification treatment on the commercial carbon fibers which are desized cleanly in advance, and comprises the following steps:

a. adopting de-sizing liquid to carry out de-sizing treatment on the original sizing agent on the surface of the carbon fiber to be treated, wherein the carbon fiber to be treated is a commercial carbon fiber which is sized with a universal sizing agent; placing the carbon fiber in an environment of 110-180 ℃ for 1-5 min, taking out, quickly placing the carbon fiber into liquid nitrogen for soaking for 5-60 s, taking out, placing the carbon fiber into de-starching liquid, ultrasonically oscillating for 15-120 min, taking out, and drying to obtain the de-starched carbon fiber;

b. and (3) re-sizing the surface of the degummed clean carbon fiber by using the composite high-temperature-resistant sizing agent for the carbon fiber to finish the re-sizing process of the carbon fiber.

Preferably, in the step a, the slurry removing liquid comprises the following components in percentage by mass: 20-40 wt% of dichloromethane, 20-40 wt% of benzyl alcohol, 10-30 wt% of methanol, 5-10 wt% of N-ethyl pyrrolidone, 0.5-3 wt% of phenol, 2-7 wt% of hydrogen peroxide and 2.5-10 wt% of cetyl trimethyl ammonium bromide serving as a surfactant.

The surfactant cetyl trimethyl ammonium bromide plays a role in the desizing process to improve the desizing effect, and the surfactant is still remained on the surface of the carbon fiber after the carbon fiber is desized and the solvent is volatilized, so that the full contact and wetting between the surfactant and the surface of the carbon fiber are ensured, the process is simplified, and the subsequent sizing effect is improved.

The second purpose of the invention is to provide a process method for sizing the composite high-temperature-resistant sizing agent after desizing of commercial carbon fibers. The key points are three:

the method comprises the following steps of (1) effectively eliminating a general sizing agent carried by commercial carbon fibers when the commercial carbon fibers leave a factory by using a desizing liquid so as to eliminate the adverse effects of the general sizing agent on a subsequent re-sizing process and the performance of a composite material;

whether the new sizing agent has stronger interface bonding effect with the carbon fiber and the polyether-ether-ketone resin or not and meets the high-temperature processing requirement in the range of 330 ℃ and 380 ℃;

and thirdly, the desizing component is directly converted into the sizing component, so that the process is simplified and the performance is improved.

Because the shrinkage rates of the carbon fiber and the epoxy resin universal sizing agent are obviously different, the bonding force between the commercial carbon fiber and the original factory sizing agent is obviously reduced through the steps of firstly heating, then soaking in low-temperature liquid nitrogen, and then placing in normal-temperature de-sizing agent. The destaining liquid can enter a gap between the two more easily, so that the destaining effect is enhanced, and the time required by the destaining process is greatly shortened.

Preferably, in the step b, the carbon fibers are preheated to 40-60 ℃ by using the composite high-temperature-resistant sizing agent, the carbon fibers which are completely degummed are placed into the composite high-temperature-resistant sizing agent for carbon fibers to be soaked for 5-30 s, the carbon fibers are taken out to scrape off redundant sizing agent, and the carbon fibers are dried for 10-60 min at the temperature of 60-100 ℃ to obtain the carbon fibers which are re-sized by using the composite high-temperature-resistant sizing agent.

A high temperature resistant matrix resin composite material or 3D printing material takes polyether ether ketone, polyphenylene sulfide sulfone, polyether sulfone, polyimide, polyetherimide or polytetrafluoroethylene high temperature resistant resin as a matrix; the composite high-temperature-resistant sizing agent prepared by the carbon fiber re-sizing process method is re-sized with the carbon fibers and the high-temperature-resistant matrix resin for extrusion granulation, or is cut into short fibers filled with the high-temperature-resistant matrix resin, the filling amount of the carbon fibers is 15-50 wt%, and the carbon fibers are subjected to hot forming at the temperature of 330-380 ℃ to obtain the carbon fiber reinforced high-temperature-resistant matrix resin composite material or the 3D printing material product, wherein the sizing agent on the surfaces of the carbon fibers cannot be decomposed in the forming process.

Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:

1. after being sheared, carbon fibers sized by the composite high-temperature resistant sizing agent are fused and blended with polyether-ether-ketone particles through an internal mixer, and then the carbon fibers and the polyether-ether-ketone particles are molded to prepare a tensile sample of the carbon fiber/polyether-ether-ketone composite material, and the mechanical property of the tensile sample is tested. Compared with commercial carbon fiber composite materials, the tensile strength of the carbon fiber composite material after being sized by the composite high-temperature resistant sizing agent is obviously improved;

2. the high-temperature-resistant sizing agent is provided for the carbon fibers filled with the high-temperature-resistant matrix resin with the reinforced processing temperature of 330-380 ℃, so that the interface effect between the carbon fibers and the resin matrix can be obviously improved, and the mechanical properties of the composite material and the 3D printing material are improved;

3. the method is simple and easy to implement, low in cost and suitable for popularization and application.

Drawings

FIG. 1 shows the comparison of the surface micro-morphology of commercial carbon fiber, carbon fiber after desizing, and carbon fiber re-sized by the composite high temperature resistant sizing agent of the present invention.

Fig. 2 is a DTG spectrogram comparison of carbon fibers sized by the composite high-temperature resistant sizing agent of the first embodiment of the present invention and commercial carbon fibers.

Fig. 3 is a comparison of tensile strength of the carbon fiber and commercial carbon fiber respectively sized by the composite high temperature resistant sizing agent of the first embodiment of the invention and a composite material prepared by polyetheretherketone.

Detailed Description

The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:

the first embodiment is as follows:

in this embodiment, the method includes a preparation method of the high temperature resistant sizing agent, a desizing process of the commercial carbon fiber, a process of repulping the high temperature resistant sizing agent to the desized commercial carbon fiber, and a process of preparing the high temperature resistant composite material, which are specifically as follows:

(1) preparing a desizing liquid:

taking a container, respectively pouring 40% of dichloromethane, 20% of benzyl alcohol, 10% of methanol, 10% of N-ethyl pyrrolidone, 3% of phenol, 7% of hydrogen peroxide and 10% of hexadecyl trimethyl ammonium bromide according to the mass ratio, uniformly stirring to prepare a destaining solution, and pouring the destaining solution into an ultrasonic cleaning machine to obtain the destaining solution for later use;

(2) preparing a composite high-temperature-resistant sizing agent:

taking another container, respectively adding 10% of polyphenylene sulfide sulfone and 80% of N, N-dimethylacetamide according to the mass ratio, heating to 60 ℃ and keeping, stirring for 10min, then respectively adding 5% of polyether sulfone and 5% of polyetherimide, continuously stirring for 20min, and forming a uniform solution which is the composite high-temperature resistant sizing agent for later use after the polymer is completely dissolved;

(3) after carbon fiber is degummed, sizing is carried out on the carbon fiber, and then the composite high-temperature-resistant sizing agent:

placing the commercial carbon fiber in an environment of 110 ℃ for 5min, taking out, quickly placing into liquid nitrogen, soaking for 60s, and taking out; then putting the carbon fibers into an ultrasonic cleaning machine filled with destarching liquid, immersing the carbon fibers into the destarching liquid, performing ultrasonic vibration for 15min, taking out and drying; then placing the carbon fiber into a composite high-temperature resistant sizing agent preheated at 60 ℃ for soaking for 30s, taking out the carbon fiber, scraping the redundant sizing agent, and drying the carbon fiber at 100 ℃ for 10min to obtain carbon fiber re-sized by the composite high-temperature resistant sizing agent;

(4) preparing a high-temperature-resistant resin-based composite material or a 3D printing material:

cutting 50% of carbon fibers newly sized by the composite high-temperature resistant sizing agent into short fibers, filling the short fibers with modified polyether-ether-ketone matrix resin, and processing and molding at 380 ℃ to obtain the high-temperature resistant matrix resin composite material.

Experimental test analysis:

taking carbon fibers newly sized by the composite high-temperature-resistant sizing agent prepared in the embodiment as test samples, carrying out experimental test analysis, and referring to fig. 1, wherein fig. 1 is a comparison of the surface micro-morphologies of commercial carbon fibers, carbon fibers after desizing and carbon fibers newly sized by the composite high-temperature-resistant sizing agent of the invention. As can be seen from fig. 1, the high-temperature resistant sizing agent for re-sizing can effectively fill up particles and grooves existing on the surface of the carbon fiber which is degummed clean, so that the surface of the carbon fiber becomes smooth, and the preparation of the subsequent composite material is facilitated. Fig. 2 is a DTG spectrogram comparing carbon fiber sized by the composite high temperature resistant sizing agent of the embodiment with commercial carbon fiber. As can be seen from FIG. 2, the weight loss of the commercial carbon fiber occurs from 200 ℃, which indicates that the general-purpose sizing agent starts to be thermally decomposed at the moment, the maximum weight loss occurs at about 360 ℃, and the general-purpose sizing agent is basically damaged at the moment; and the carbon fiber sizing agent of the high-temperature resistant sizing agent begins to lose weight at 400 ℃, and the maximum weight loss occurs at 450 ℃, which shows that the high-temperature resistant sizing agent can completely adapt to the processing temperature of 330-380 ℃. Fig. 3 is a comparison of the tensile strength of the carbon fiber and commercial carbon fiber respectively sized by the composite high temperature resistant sizing agent in the present embodiment and the composite material prepared by polyetheretherketone. As can be seen from fig. 3, the tensile property of the polyetheretherketone composite material filled with carbon fibers and sized with the high temperature resistant sizing agent of the present invention is significantly improved compared to the commercial carbon fiber filled composite material. The embodiment illustrates that the composite high-temperature-resistant sizing provided by the embodiment can adapt to the processing temperature of the high-temperature-resistant matrix resin, cannot be pyrolyzed and damaged during processing, can obviously improve the interface effect between the carbon fiber and the resin matrix, and improves the mechanical properties of the composite material and the 3D printing material.

Example two:

in this embodiment, the method includes a preparation method of the high temperature resistant sizing agent, a desizing process of the commercial carbon fiber, a process of repulping the high temperature resistant sizing agent to the desized commercial carbon fiber, and a process of preparing the high temperature resistant composite material, which are specifically as follows:

(1) preparing a desizing liquid:

taking a container, respectively pouring 20% of dichloromethane, 40% of benzyl alcohol, 30% of methanol, 5% of N-ethyl pyrrolidone, 0.5% of phenol, 2% of hydrogen peroxide and 2.5% of hexadecyl trimethyl ammonium bromide according to the mass ratio, uniformly stirring to prepare a destaining solution, and pouring the destaining solution into an ultrasonic cleaning machine for later use;

(2) preparing a composite high-temperature-resistant sizing agent:

taking a container, respectively adding 0.2% of polyphenylene sulfide sulfone and 99.6% of N-ethyl pyrrolidone according to the mass ratio, heating to 40 ℃ and keeping, stirring for 5min, respectively adding 0.1% of polyether sulfone and 0.1% of polyether imide, continuously stirring for 10min, and forming a uniform solution which is the composite high-temperature resistant sizing agent for standby after the compound is completely dissolved;

(3) after carbon fiber is degummed, sizing is carried out on the carbon fiber, and then the composite high-temperature-resistant sizing agent:

placing commercial carbon fiber in an environment of 180 ℃ for 1min, taking out, rapidly placing into liquid nitrogen for soaking for 5s, and taking out; then putting the carbon fibers into an ultrasonic cleaning machine filled with destarching liquid, immersing the carbon fibers into the destarching liquid, carrying out ultrasonic vibration for 120min, taking out the carbon fibers and drying the carbon fibers; soaking in 40 deg.C preheated composite high temperature resistant sizing agent for 5s, taking out, scraping off excessive sizing agent, and drying at 60 deg.C for 60min to obtain carbon fiber re-sized with composite high temperature resistant sizing agent;

(4) preparation of high-temperature-resistant resin-based composite material or 3D printing material

Cutting 15% of carbon fiber re-sized by the composite high-temperature resistant sizing agent into short fibers, filling modified polyphenylene sulfide matrix resin, and processing and molding at 330 ℃.

Example three:

in this embodiment, the preparation method of the high temperature resistant sizing agent, the desizing process of the commercial carbon fiber, and the process of repulping the high temperature resistant sizing agent to the desized commercial carbon fiber are specifically as follows:

(1) preparing a desizing liquid:

taking a container, respectively pouring 30% of dichloromethane, 30% of benzyl alcohol, 20% of methanol, 8% of N-ethyl pyrrolidone, 2% of phenol, 5% of hydrogen peroxide and 5% of hexadecyl trimethyl ammonium bromide according to the mass ratio, uniformly stirring, preparing into destaining liquid, and pouring into an ultrasonic cleaning machine for later use;

(2) preparing a composite high-temperature-resistant sizing agent:

and taking another container, respectively adding 5% of polyphenylene sulfide sulfone and 90% of sulfolane according to the mass ratio, heating to 50 ℃, keeping the temperature, and stirring for 8 min. Then respectively adding 2% of polyether sulfone and 3% of polyetherimide, continuously stirring for 15min, and forming a uniform solution after the polymer is completely dissolved, namely the composite high-temperature resistant sizing agent for later use;

(3) after carbon fiber is degummed, sizing is carried out on the carbon fiber, and then the composite high-temperature-resistant sizing agent:

placing the commercial carbon fiber in an environment of 145 ℃ for 3min, taking out, quickly placing into liquid nitrogen, soaking for 30s, and taking out; then putting the carbon fibers into an ultrasonic cleaning machine filled with destarching liquid, immersing the carbon fibers under the destarching liquid surface, ultrasonically vibrating for 60min, taking out and drying; soaking in a composite high-temperature resistant sizing agent preheated at 50 ℃ for 20s, taking out, scraping off redundant sizing agent, and drying at 80 ℃ for 35min to obtain carbon fiber re-sized by the composite high-temperature resistant sizing agent;

(4) preparation of high-temperature-resistant resin-based composite material or 3D printing material

And (2) extruding and granulating the carbon fiber re-sized by the composite high-temperature resistant sizing agent and the polyphenylene sulfide sulfone matrix resin together according to the mass ratio of 32%, and preparing the 3D printing material at the processing temperature of 360 ℃.

In summary, the present invention relates to a composite high temperature resistant sizing agent for sizing the surface of reinforced carbon fiber for preparing composite material with polyetheretherketone, polyphenylene sulfide sulfone, polyethersulfone, polyimide, polyetherimide or polytetrafluoroethylene as matrix and 3D printing material, and an application method thereof: the preparation method comprises a preparation method of the high-temperature-resistant sizing agent, a desizing process of the commercial carbon fiber, a process of repulping the high-temperature-resistant sizing agent to the desized commercial carbon fiber, and preparation process parameter setting of the composite material and the 3D printing material. The high-temperature resistant sizing agent comprises the following components in percentage by mass: 0.2-10 wt% of polyphenylene sulfide sulfone, 0.1-5 wt% of polyether sulfone, 0.1-5 wt% of polyetherimide and 80-99.6 wt% of organic solvent. The high-temperature-resistant sizing agent is provided for the carbon fibers filled with the high-temperature-resistant matrix resin with the reinforced processing temperature of 330-380 ℃, so that the interface effect between the carbon fibers and the resin matrix can be obviously improved, and the mechanical properties of the composite material and the 3D printing material are improved.

The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.