Polyether ketone resin product and production method thereof

Abstract

The invention discloses a production method of a polyetheretherketone resin product. The production method comprises the following steps: step S100, providing polyetheretherketone prepolymerized resin; step S200, providing a cross-linking agent with a primary amine group; step S300, mixing the polyether-ether-ketone pre-polymerized resin and a cross-linking agent, and performing granulation to obtain a precursor; and S400, carrying out injection molding treatment on the precursor, keeping the precursor in a predetermined three-dimensional shape, and carrying out crosslinking treatment to obtain a product, and S500, the product is subjected to annealing treatment. According to the preparation method disclosed by the invention, a crosslinkable side chain with strong rigidity is introduced on the premise of not influencing or slightly influencing the crystallinity of the prepolymerization raw material of the polyether-ether-ketone resin with high crystallinity, so that the high-temperature modulus of the prepolymerization raw material at the temperature of 250-340 DEG C is mainly enhanced, and the heat resistance, the high-temperature modulus and the high-temperature mechanical property of the resin are remarkably enhanced; and the device can be applied to a high-temperature special working environment.

Description

Technical Field

[0001] The present application relates to the field of polymer synthesis, and in particular to a polyetherketone resin product and a production method thereof. Background Art

[0002] Polyetheretherketone (PEEK) is a special polymer material with a large number of applications in the aerospace field, medical device field (as artificial bone to repair bone defects) and industrial field. In addition, polyetheretherketone (PEEK) is also a crystalline polymer. Compared with non-crystalline polymers, it has higher strength, rigidity and stability, and the processing performance of crystalline polymers is better. The crystallinity of the crystalline region after molding is not easily affected by thermal expansion, and it has excellent heat resistance. It can continue to be used at high temperatures without decomposition or failure, which makes it have excellent mechanical properties, hot melt and chemical stability. It has been widely used in industries, agriculture and home furnishings. However, the glass transition temperature of polyetheretherketone resin is only 143℃, which is not too high in the field of special polymers. The application of polyetheretherketone is subject to some restrictions. For example, in special working environments of 200℃ to 220℃ or even higher temperatures, polyetheretherketone resin will soften, that is, the intermolecular force is weak at high temperature, resulting in low high-temperature modulus, which in turn reduces its mechanical properties at high temperatures, thereby greatly limiting the high-temperature application of polyetheretherketone.

[0003] In order to further enhance its heat resistance, high temperature modulus, and high temperature mechanical properties without significantly reducing its crystallinity or slightly reducing its crystallinity, the present application creatively synthesizes a side chain cross-linked polyetheretherketone resin and makes it into a product at the same time as the synthetic resin, which can be used in special working environments with high temperatures. Summary of the invention

[0004] In order to enhance the heat resistance, high temperature modulus and high temperature mechanical properties of polyetheretherketone resin without affecting or slightly reducing the crystallinity, the present application provides a polyetheretherketone resin product and a production method thereof. The obtained polyetheretherketone resin product has strong heat resistance, significantly improved high temperature modulus and excellent high temperature mechanical properties, and can be used in special working environments with high temperatures.

[0005] The present application provides a method for producing a polyetherketone resin product, comprising the following steps:

[0006] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0007] Where n>1;

[0008] Step S200: providing a cross-linking agent with a primary amine group;

[0009] Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent and granulating them to obtain a precursor;

[0010] Step S400: injecting the precursor and keeping it in a predetermined three-dimensional shape and cross-linking it to obtain a product;

[0011] Step S500: performing annealing treatment on the product.

[0012] In the present application, a prepolymer raw material of a polyetheretherketone resin with a high crystallinity is first melt-mixed and granulated with a cross-linking agent. The melt-mixing process is very short, mainly to allow the two to be fully mixed. Although local cross-linking may occur, the proportion is very small, and a longer period of sufficient thermal cross-linking treatment is required, that is, the primary amine (R-NH2) reacts with the oxygen atom of the ketone carbonyl group to produce a ketoamine reaction, so that the side chain can be added to the main chain structure of the prepolymer resin. Finally, without affecting or slightly reducing the crystallinity of the prepolymer raw material, cross-linkable rigid side chains are introduced to enhance heat resistance and structural stability.

[0013] In addition, since the glass transition temperature of the polyetheretherketone prepolymer resin is 143°C, its mechanical properties are poor in a temperature environment of 200°C and above. The side chain cross-linked polyetheretherketone resin of the present application mainly enhances its high-temperature modulus in the temperature range of 250°C to 340°C, significantly enhancing its high-temperature mechanical properties, so that it can be used in special high-temperature working environments.

[0014] Based on the above-mentioned synthetic side-chain cross-linked polyetheretherketone resin with high heat resistance and excellent high-temperature modulus, in order to meet the needs of manufacturing various three-dimensional shaped products in the field of special materials, the present application directly injects the precursor into the mold for pre-molding and demolding. Since the entire injection molding process (including from melting to cooling to room temperature) is very short (only tens of seconds), only a very small part of micro-crosslinking is produced inside the precursor. It can be seen that the injection molding and shaping treatment of the precursor is mainly for shaping under a state of no internal stress or very small internal stress.

[0015] The precursor after demoulding is fully cross-linked in the stage of treatment, so that after the cross-linking is completed, a product with uniform stress distribution can be directly obtained, thereby improving the fatigue resistance of the product.

[0016] Optionally, the general structural formula of the cross-linking agent is:

[0017]

[0018] Optionally, the preparation method of the cross-linking agent comprises the following steps:

[0019] Step S201: Take X mol of anhydride monomer, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 100° C. to 120° C.;

[0020] Step S202: After the anhydride monomer is completely melted, Z mol of diamine monomer is poured into the mixture several times to obtain a mixed solution and stirred, and the mixed solution is kept at a temperature of 120° C. to 130° C. for 3 to 4 hours, wherein the ratio of X, Y, and Z is (0.95 to 1.05): 1:40;

[0021] Step S203: washing the mixed solution with ethanol and water for more than 3 times, and then vacuum drying to obtain a cross-linking agent.

[0022] Optionally, the diamine monomer is p-phenylenediamine or m-phenylenediamine; and the anhydride monomer is phenylethynylphthalic anhydride.

[0023] In the preparation method of the cross-linking agent, the anhydride monomer, namely phenylethynyl phthalic anhydride, is directly cyclized in acetic acid at high temperature, which can eliminate the interference of chemical cyclization small molecule reagents and by-products, making post-processing simpler and the product purer.

[0024] Optionally, in step S300, the cross-linking agent and the polyetheretherketone prepolymer resin are mixed and granulated in a molar ratio of (0.1-30):100.

[0025] Optionally, in step S300, the working temperature of the granulation is 300°C to 350°C, and the temperature of the injection molding process is 330°C to 380°C.

[0026] Optionally, the cross-linking treatment in step S400 is a step-wise temperature increase process in a nitrogen atmosphere, including:

[0027] First, heat from room temperature to 240°C and keep warm for 0.01 to 1 hour;

[0028] Then raise the temperature to 290°C and keep it at this temperature for 0.01 to 2 hours;

[0029] Finally, the temperature is raised to 340°C and kept at this temperature for 0.01 to 5 hours.

[0030] This application chooses to perform cross-linking treatment in a nitrogen atmosphere. Due to the stable chemical properties of nitrogen, it can effectively prevent the resin from being oxidized at high temperatures, thereby protecting the purity and performance of the resin. In addition, the step-by-step heating process gradually increases the temperature, allowing the resin to gradually adapt to temperature changes, avoiding the concentration of thermal stress that may be caused by direct high-temperature heating, thereby achieving a more uniform heating process and more complete cross-linking.

[0031] Optionally, the annealing process in step S500 includes:

[0032] After the cross-linking treatment of the product is completed, the temperature is first lowered to 240° C. to 290° C. and kept at this temperature for 0.5 to 10 hours, and then the product is naturally cooled to room temperature.

[0033] The present application also discloses a polyetherketone resin product, which is prepared according to the above production method. The polyetheretherketone prepolymer resin and the cross-linking agent with a primary amine group are generated by nucleophilic addition-dehydration reaction. The polyetherketone resin product contains the following repeating segments:

[0034] Where n>1.

[0035] Optionally, the glass transition temperature of the polyetherketone resin product is 160-180°C.

[0036] Optionally, the crystallinity of the polyetheretherketone resin product decreases by no more than 5% compared with the polyetheretherketone prepolymer resin.

[0037] Optionally, the heat deformation temperature of the polyetherketone resin product is 340-380°C.

[0038] Optionally, the high temperature modulus of the polyetherketone resin product at 320° C. is 300 to 3000 MPa.

[0039] The polyether ketone resin product finally obtained in the present application has a higher glass transition temperature than the initial prepolymer resin (polyether ether ketone resin Tg is generally 143°C), the degree of crystallinity is affected very limitedly, that is, the decrease in crystallinity does not exceed 5%, and the heat resistance is also significantly higher than the prepolymer resin, especially in the temperature range of 250°C to 340°C, the high-temperature modulus is significantly improved, and the high-temperature mechanical properties are significantly enhanced, thereby making it more applicable in the field of special polymers.

[0040] Optionally, the predetermined three-dimensional shape of the product has at least one bending portion.

[0041] Optionally, the predetermined three-dimensional shape of the product is columnar or cylindrical.

[0042] The bending part can be a relatively smooth curved surface, such as a cylindrical or tubular arc surface, or a fold or step with a more obvious trend. During injection molding pre-forming, the product can be kept in a predetermined three-dimensional shape by using mold support or other methods, that is, the precursor is first melted and injected into a mold that matches the predetermined three-dimensional shape and then quickly cooled to room temperature for final shaping. When cross-linking is completed, the entire product or at least the bending part is in a state of uniform stress distribution, which improves the fatigue resistance of the bending part. For the convenience of operation, the entire product and even the mold can be placed in a high temperature environment for cross-linking treatment.

[0043] In order to solve the problem of poor fatigue resistance of polymers, the present application performs three-dimensional shaping when there is no internal stress or very small internal stress in the whole product or at least in the bending parts, thereby optimizing the stress distribution of the product and improving the fatigue resistance of the product film. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is a schematic diagram of the structure of the product;

[0045] Figure 2 This is the DSC curve of the side chain cross-linked polyetheretherketone resin prepared in Example 3. DETAILED DESCRIPTION

[0046] Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of this application.

[0047] An embodiment of the present application provides a method for producing a polyetherketone resin product in order to enhance heat resistance, high temperature modulus, and high temperature mechanical properties without affecting crystallinity or slightly reducing crystallinity, comprising the following steps:

[0048] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0049] Where n>1;

[0050] Step S200: providing a cross-linking agent with a primary amine group, that is, its structural formula can be understood as R-NH2;

[0051] Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent and granulating them to obtain a precursor;

[0052] Step S400: injecting the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking to obtain a product;

[0053] Step S500: performing annealing treatment on the product.

[0054] The polyetheretherketone prepolymer resin used in this embodiment is a polymer composed of a repeating unit containing a ketone bond and two ether bonds in the main chain structure. It is a special polymer material with physical and chemical properties such as high temperature resistance and chemical corrosion resistance. It is a type of semi-crystalline polymer material that can be used as a high temperature resistant structural material and electrical insulating material, and can be composited with glass fiber or carbon fiber to prepare reinforcing materials. Generally, a type of polyarylether polymer obtained by condensation with aromatic dihydric phenol is used. This material has a large number of applications in the fields of aerospace, medical equipment (as artificial bone to repair bone defects) and industry.

[0055] The cross-linking agent with a primary amine group used in this embodiment can react with the ketone bond in the prepolymer resin through nucleophilic addition-dehydration reaction to generate a side-chain cross-linked polyetheretherketone resin (i.e., the primary amine (R-NH2) reacts with the oxygen atom of the ketone carbonyl group to form a ketoamine reaction), thereby introducing high-rigidity side chains while maintaining high crystallinity to the greatest extent, mainly enhancing its high-temperature modulus in the temperature range of 250°C to 340°C, and significantly enhancing the heat resistance, high-temperature modulus, and high-temperature mechanical properties of the resin, so that it can be used in special high-temperature working environments.

[0056] In order to further optimize the stress distribution within the product and improve the fatigue resistance of the product, the present application directly injects the precursor of the side-chain cross-linked polyetheretherketone resin into the mold for pre-molding, rapid cooling, and demolding. That is, the precursor is pre-molded under a state of no internal stress or very small internal stress and then cross-linked and annealed. Therefore, after the cross-linking is completed, a product with uniform stress distribution can be directly obtained, which has higher stability and reduces the separate process of making three-dimensional products from flat films.

[0057] In some embodiments, the cross-linking agent has the general formula:

[0058]

[0059] Among them, the general structural formula can be understood to include the following two specific structural formulas, namely

[0060]

[0061] In some embodiments, the method for preparing the cross-linking agent comprises the following steps:

[0062] Step S201: Take X mol of anhydride monomer, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 100° C. to 120° C.;

[0063] Step S202: After the anhydride monomer is completely melted, Z mol of diamine monomer is poured in two or more times to obtain a mixed solution and stirred. When the temperature is raised to 120° C. to 130° C., reflux treatment is performed, and the mixed solution is maintained at 120° C. to 130° C. for 3 to 4 hours, wherein the molar ratio of X, Y, and Z is (0.95 to 1.05): 1:40;

[0064] Step S203: washing the mixed solution with ethanol and water for more than three times, and then vacuum drying to obtain a cross-linking agent.

[0065] In some embodiments, the diamine monomer is p-phenylenediamine or m-phenylenediamine; and the anhydride monomer is phenylethynylphthalic anhydride.

[0066] In some embodiments, in step S300, the cross-linking agent and the polyetheretherketone prepolymer resin are mixed and granulated in a molar ratio of (0.1-30):100.

[0067] In some embodiments, in step S300, the working temperature of granulation is 300°C to 350°C, and the temperature of injection molding is 330°C to 380°C, that is, the temperature of melting the precursor particles is 330°C to 380°C, but the time when the precursor is in a molten state during the injection molding process is very short, only about tens of seconds, and it is quickly cooled immediately after the injection molding is completed. It can be understood that almost no cross-linking occurs inside the precursor during the injection molding process, or a very small part of it occurs cross-linking.

[0068] In some embodiments, the cross-linking process in step S400 is a step-wise temperature increase process in a nitrogen atmosphere, including:

[0069] First, heat from room temperature to 240°C and keep warm for 0.01 to 1 hour;

[0070] Then raise the temperature to 290°C and keep it at this temperature for 0.01 to 2 hours;

[0071] Finally, the temperature is raised to 340°C and kept at this temperature for 0.01 to 5 hours.

[0072] In some embodiments, the annealing process in step S500 includes:

[0073] After the cross-linking treatment of the product is completed, the temperature is first lowered to 240°C to 290°C and kept warm for 0.5 to 10 hours, and then the product is naturally cooled to room temperature.

[0074] The present application also discloses a polyetherketone resin product, which is prepared according to the production method described in the above embodiment, and is produced by a nucleophilic addition-dehydration reaction of a polyetheretherketone prepolymer resin and a crosslinking agent with a primary amine group. The polyetherketone resin product contains the following repeating segments:

[0075] Where n>1.

[0076] Among them, the general structural formula can be understood to include the following two specific structural formulas, namely

[0077]

[0078] In some embodiments, the polyetherketone resin article has a glass transition temperature of 160-180°C.

[0079] In some embodiments, the crystallinity of the polyether ketone resin product is reduced by no more than 5% compared with the polyether ether ketone prepolymer resin, and the reduction is mainly controlled at 1% to 2%. The crystallinity is generally 19% to 28%. The crystallinity can be Figure 2 Calculated from the DSC curve shown.

[0080] The heat deformation temperature of polyetherketone resin products is 340-380°C. The high temperature modulus of polyetherketone resin products at 320°C is 300-3000MPa, mainly concentrated between 500-2000.

[0081] In some embodiments, the article has a predetermined three-dimensional shape with at least one bend. Figure 1 The structural diagram of the product in the figure, the bending part of the predetermined three-dimensional shape of the product can be a relatively smooth curved surface, such as a cylindrical or cylindrical arc surface, or it can be a fold or step with a more obvious trend. During the pre-molding, the product can be maintained in a predetermined three-dimensional shape by using mold support and other methods, that is, the precursor is first melt-molded into a mold that matches the predetermined three-dimensional shape and quickly cooled, so that the precursor can be maintained in the predetermined three-dimensional shape. Then, a thermal cross-linking treatment is performed. After the cross-linking is completed, the entire product or at least the bending part is in a state of uniform stress distribution, thereby improving the fatigue resistance of the bending part.

[0082] Example 1

[0083] The production method of polyetherketone resin products comprises the following steps:

[0084] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0085] Where n>1;

[0086] Step S200: providing a cross-linking agent with a primary amine group, wherein the preparation method of the cross-linking agent comprises the following steps:

[0087] Step S201: Take X mol of phenylethynylphthalic anhydride, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 100° C.;

[0088] Step S202: After all the phenylethynylphthalic anhydride is melted, Z mol of p-phenylenediamine is poured into the mixture in two or more portions to obtain a mixed solution, which is stirred and refluxed when heated to 120° C. The mixed solution is kept at 120° C. for 3 hours, wherein the ratio of X, Y, and Z is 0.95:1:40;

[0089] Step S203: washing the mixed solution with ethanol and water for more than 3 times, and then vacuum drying to obtain a cross-linking agent;

[0090] Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent in a molar ratio of 0.1:100 and granulating the mixture at a granulation temperature of 300° C. to obtain a precursor of a side chain cross-linked polyetheretherketone resin;

[0091] Step S400: performing an injection molding process on the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking treatment, wherein the cross-linking treatment is a step-by-step temperature increase process in a nitrogen atmosphere, including:

[0092] First, heat from room temperature to 240°C and keep warm for 0.01 hour;

[0093] Then raise the temperature to 290°C and keep it for 0.01 hour;

[0094] Finally, the temperature was raised to 340°C and kept at this temperature for 0.01 hour;

[0095] Step S500: annealing the product, that is, first cooling the product to 240° C. and keeping it at this temperature for 5 hours, and then naturally cooling the product to room temperature.

[0096] Example 2

[0097] The production method of polyetherketone resin products comprises the following steps:

[0098] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0099] Where n>1;

[0100] Step S200: providing a cross-linking agent with a primary amine group, wherein the preparation method of the cross-linking agent comprises the following steps:

[0101] Step S201: Take X mol of phenylethynylphthalic anhydride, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 120° C.;

[0102] Step S202: After all the phenylethynylphthalic anhydride is melted, Z mol of p-phenylenediamine is poured into the mixture in two or more portions to obtain a mixed solution, which is stirred and refluxed when the temperature is raised to 130° C. The mixed solution is kept at 130° C. for 4 hours, wherein the ratio of X, Y, and Z is 1.05:1:40;

[0103] Step S203: washing the mixed solution with ethanol and water for more than 3 times, and then vacuum drying to obtain a crosslinking agent; Step S300: mixing the polyetheretherketone prepolymer resin and the crosslinking agent in a molar ratio of 30:100 and granulating at a granulation temperature of 350° C. to obtain a precursor of a side chain crosslinked polyetheretherketone resin;

[0104] Step S400: performing an injection molding process on the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking treatment, wherein the cross-linking treatment is a step-by-step temperature increase process in a nitrogen atmosphere, including:

[0105] First, heat from room temperature to 240℃ and keep warm for 1 hour;

[0106] Then raise the temperature to 290°C and keep it for 2 hours;

[0107] Then raise the temperature to 340°C and keep it for 5 hours;

[0108] Step S500: annealing the product, that is, first cooling the product to 290° C. and keeping the temperature for 10 hours, and then naturally cooling the product to room temperature.

[0109] Example 3

[0110] The production method of polyetherketone resin products comprises the following steps:

[0111] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0112] Where n>1;

[0113] Step S200: providing a cross-linking agent with a primary amine group, wherein the preparation method of the cross-linking agent comprises the following steps:

[0114] Step S201: Take X mol of phenylethynylphthalic anhydride, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 110° C.;

[0115] Step S202: After all the phenylethynylphthalic anhydride is melted, Z mol of p-phenylenediamine is poured into the mixture in two or more portions to obtain a mixed solution, which is stirred. When the temperature is raised to 120° C. to 130° C., the mixed solution is refluxed and maintained at 125° C. for 3.5 hours, wherein the ratio of X, Y, and Z is 1:1:40;

[0116] Step S203: washing the mixed solution with ethanol and water for more than 3 times, and then vacuum drying to obtain a cross-linking agent;

[0117] Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent in a molar ratio of 15:100 and granulating the mixture at a granulation temperature of 325 to obtain a precursor of a side chain cross-linked polyetheretherketone resin;

[0118] Step S400: performing an injection molding process on the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking treatment, wherein the cross-linking treatment is a step-by-step temperature increase process in a nitrogen atmosphere, including:

[0119] First, heat from room temperature to 240°C and keep warm for 0.5 hours;

[0120] Then raise the temperature to 290°C and keep it for 1 hour;

[0121] Finally, the temperature was raised to 340°C and kept at this temperature for 2.5 hours;

[0122] Step S500: annealing the product, that is, first cooling the product to 260° C. and keeping it at this temperature for 8 hours, and then naturally cooling the product to room temperature.

[0123] Example 4

[0124] The production method of polyetherketone resin products comprises the following steps:

[0125] Step S100: providing a polyetheretherketone prepolymer resin having the structural formula:

[0126] Where n>1;

[0127] Step S200: providing a cross-linking agent with a primary amine group, wherein the preparation method of the cross-linking agent comprises the following steps:

[0128] Step S201: Take X mol of phenylethynylphthalic anhydride, pour it into Y mol of glacial acetic acid, introduce nitrogen and heat to 120° C.;

[0129] Step S202: After all the phenylethynylphthalic anhydride is melted, Z mol of m-phenylenediamine is poured into the mixture in two or more portions to obtain a mixed solution, which is stirred and refluxed when the temperature is raised to 130° C. The mixed solution is kept at 130° C. for 4 hours, wherein the ratio of X, Y, and Z is 1.05:1:40;

[0130] Step S203: washing the mixed solution with ethanol and water for more than 3 times, and then vacuum drying to obtain a cross-linking agent;

[0131] Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent in a molar ratio of 30:100 and granulating the mixture at a granulation temperature of 350° C. to obtain a precursor of a side chain cross-linked polyetheretherketone resin;

[0132] Step S400: performing an injection molding process on the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking treatment, wherein the cross-linking treatment is a step-by-step temperature increase process in a nitrogen atmosphere, including:

[0133] First, heat from room temperature to 240℃ and keep warm for 1 hour;

[0134] Then raise the temperature to 290°C and keep it for 2 hours;

[0135] Finally, the temperature was raised to 340°C and kept at this temperature for 5 hours;

[0136] Step S500: annealing the product, that is, first cooling the product to 290° C. and keeping the temperature for 10 hours, and then naturally cooling the product to room temperature.

[0137] Example 5

[0138] Take the products of the above embodiments and use polyetheretherketone prepolymer resin as comparative example 1 to test the glass transition temperature, crystallinity, room temperature modulus, high temperature modulus, room temperature tensile strength and high temperature tensile strength. The data are recorded in Table 1 below.

[0139] Table 1

[0140]

[0141] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0142] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent application. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application.

Claims

1. A method for producing a polyetherketone resin product, characterized in that: The following steps are involved: Step S100: providing a polyetheretherketone prepolymer resin having the structural formula: Where n>1; Step S200: providing a cross-linking agent with a primary amine group; Step S300: mixing the polyetheretherketone prepolymer resin and the cross-linking agent and granulating them to obtain a precursor; Step S400: injecting the precursor and maintaining it in a predetermined three-dimensional shape for cross-linking to obtain a product; Step S500: performing annealing treatment on the product.

2. The production method according to claim 1, characterized in that The general structural formula of the cross-linking agent is:

3. The production method according to claim 1, characterized in that In step S300, the cross-linking agent and the polyetheretherketone prepolymer resin are mixed and granulated in a molar ratio of (0.1-30):

100.

4. The production method according to claim 3, characterized in that: In step S300, the working temperature of granulation is 300°C to 350°C, and the temperature of the injection molding process is 330°C to 380°C.

5. The production method according to claim 1, characterized in that: The cross-linking process in step S400 is a step-wise temperature increase process in a nitrogen atmosphere, including: First, heat from room temperature to 240°C and keep warm for 0.01 to 1 hour; Then raise the temperature to 290°C and keep it at this temperature for 0.01 to 2 hours; Finally, the temperature is raised to 340°C and kept at this temperature for 0.01 to 5 hours.

6. The production method according to claim 1, characterized in that: The annealing process in step S500 includes: After the cross-linking treatment of the product is completed, the temperature is first lowered to 240° C. to 290° C. and kept at this temperature for 0.5 to 10 hours, and then the product is naturally cooled to room temperature.

7. A polyetherketone resin product, characterized in that: The polyetheretherketone prepolymer resin and the cross-linking agent with a primary amine group are reacted by nucleophilic addition-dehydration reaction, and the polyetherketone resin product contains the following repeating segments: Where n>

1.

8. The polyetherketone resin product according to claim 7, characterized in that: The crystallinity of the polyether ketone resin product is reduced by no more than 5% compared with the polyether ether ketone prepolymer resin.

9. The polyetherketone resin product according to claim 8, characterized in that: The high temperature modulus of the polyetherketone resin product at 320° C. is 300-3000 MPa.

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