Preparation method of high-molecular-weight polyketone resin capable of being subjected to injection molding processing, composite material of high-molecular-weight polyketone resin and preparation method of composite material

Abstract

The invention relates to a preparation method of high-molecular-weight polyketone resin capable of being subjected to injection molding processing, a composite material and a preparation method thereof. The method comprises the following steps: catalyzing ternary polymerization of ethylene, carbon monoxide and long-chain olefin by using a nickel catalyst to prepare high-molecular-weight polyketone; the polyketone resin composite material comprises the following components in parts by mass: 79-98 parts of polyketone, 0.1-5 parts of a heat stabilizer, 0.1-2 parts of an antioxidant, 1-20 parts of a plasticizer and 0.1-1 part of a lubricant. The nickel catalyst can efficiently catalyze the reaction under mild conditions to obtain ternary polyketone with the molecular weight of 200kg mol <-1 >-400kg mol <-1 >, and meanwhile, the polyketone resin composite material is prepared from polyketone, a heat stabilizer, an antioxidant, a plasticizer and a lubricant, so that the processing stability can be improved, the curing cross-linking phenomenon can be reduced, the thermal side reaction can be inhibited, the melt flowability can be improved, and the production cost can be reduced. Therefore, the processability of the high-molecular-weight polyketone is enhanced, and excellent physical and mechanical properties of the polyketone are ensured.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials and relates to a preparation method of a high molecular weight polyketone resin capable of injection molding, a composite material thereof, and a preparation method thereof. Background Art

[0002] Polyketone is a semi-crystalline engineering plastic formed by the alternating copolymerization of inexpensive olefins (such as ethylene, propylene, etc.) and carbon monoxide (CO). As one of the main raw materials, the waste gas CO is usually burned to form carbon dioxide for emission treatment, which fails to achieve the purpose of emission reduction. In the production of polyketone, 50000MT of PK can consume 250000MT of CO, which not only realizes the efficient utilization of inexpensive waste gas but also makes polyketone with excellent properties have a lower raw material cost than other engineering plastics. Polyketone not only has a regular structure, high crystallinity, chemical corrosion resistance, gas barrier property, and high temperature resistance but also has excellent mechanical properties. Compared with engineering plastics such as polyoxymethylene (POM), nylon (Nylon), polybutylene terephthalate (PBT), and polycarbonate (PC), polyketone has significant advantages in terms of wear resistance, toughness, and impact strength.

[0003] Among them, the molecular weight, as a core performance index of polyketone, directly determines the difference in its application fields. By precisely regulating the molecular weight, polyketone can obtain ideal injection molding and extrusion processing properties while maintaining excellent mechanical properties. In previous reports, the preparation of high molecular weight polyketone mostly focused on ethylene / propylene / CO terpolyketone, and the catalysts used were mostly noble metal palladium-based metals. For example, the organometallic complexes of divalent palladium salts and bidentate phosphine ligands were used in patents CN114106318A and CN113912836A. Nickel, as a substitute metal for palladium, is rich in content and inexpensive and easy to obtain. Its corresponding catalyst shows the characteristic of not being prone to chain transfer compared with palladium catalysts, making it possible to catalytically copolymerize long-chain α-olefins with ethylene / CO to prepare high molecular weight terpolyketone resin materials, thus having important research value. However, high molecular weight polyketone resin faces serious processing limitation problems during the melt processing. This is mainly due to three key factors: firstly, its melting temperature is too close to the decomposition temperature, and the processing window is extremely narrow; secondly, the carbonyl structure in the polymer chain is prone to intermolecular and intramolecular aldol condensation reactions at high temperatures, resulting in the formation of cross-linked structures; thirdly, its higher molecular weight means longer molecular chains, stronger chain entanglement, and higher melt viscosity. The narrow processing window, the occurrence of cross-linking reactions, and the increase in melt viscosity greatly increase the processing difficulty of high molecular weight polyketone, making it unable to exert its original excellent mechanical properties. Summary of the Invention

[0004] Based on the above problems, the object of the present invention is to provide a preparation method of a high molecular weight polyketone resin that can be injection-molded. By using a cheap nickel complex to catalyze the copolymerization of long-chain α-olefins (such as propylene, 1-butene, 1-hexene, 1-octene, etc.), ethylene, and CO, a terpolyketone with a molecular weight in the range of 200 kg / mol -1 to 400 kg / mol -1 is obtained. Then, additives are added to obtain a polyketone resin composite material, and finally, the processing of high molecular weight polyketone is realized.

[0005] The technical solution of the present invention:

[0006] A preparation method of a high molecular weight polyketone resin that can be injection-molded is as follows:

[0007] The structure of the catalyst used is as follows:

[0008]

[0009] The structure of the polyketone resin is as follows:

[0010]

[0011] Among them, R is an olefin within C3-C10, including propylene, 1-butene, 1-hexene, 1-octene, and 1-decene.

[0012] The molecular weight of the polyketone is in the range of 200-400 kg / mol, the molecular weight distribution is between 1.5 and 3.0, and the melting point is in the range of 200-250 °C.

[0013] The synthesis route of the high molecular weight polyketone resin is as follows:

[0014]

[0015] The steps are as follows: In a glove box, dissolve the nickel catalyst and the chain transfer reagent in a solvent to obtain a homogeneous solution; transfer the obtained solution to a mechanical stirring kettle through a feeding tank, start stirring, introduce an olefin within C3-C10, and after the temperature rises to the required temperature, charge a mixture of ethylene and carbon monoxide with a volume ratio of 1:1 at a certain pressure into the mechanical stirring kettle. After the reaction ends, cool the reaction kettle. After it returns to room temperature, release the remaining gas in the mechanical stirring kettle, and add a methanol solvent to quench the polymerization reaction. After filtration and drying, the polyketone resin is obtained.

[0016] Among them, the chain transfer reagent is one or a mixture of two or more of methanol, tert-butanol, propylene glycol, benzyl alcohol, hydrogen, lithium triisobutylborohydride, and sodium trimethoxyborohydride. The molar ratio of the chain transfer reagent to the nickel catalyst is (10-1000):1, preferably (200-800):1.

[0017] The reaction temperature in the mechanical stirring kettle is 70-130 °C, preferably 70-90 °C.

[0018] The reaction pressure in the mechanical stirring kettle is 1-6 Mpa, preferably 3-5 Mpa.

[0019] The reaction time in the mechanical stirring kettle is 0.5-12 h, preferably 0.5-8 h.

[0020] The stirring speed in the mechanical stirring kettle is 100-800 r / min, preferably 300-600 r / min.

[0021] The molar ratio of olefin within C3-C10 to carbon monoxide used in the reaction in the mechanical stirring kettle is (1-100):1, preferably (5-40):1.

[0022] The solvent is one or a mixture of two or more of toluene, dichloromethane, methanol, methyl tert-butyl ether, chlorobenzene, n-hexane, cyclohexane, and tetrahydrofuran, and the concentration of the nickel catalyst therein is 0.1-1 mmol / L -1 .

[0023] A high molecular weight polyketone resin composite material that can be injection-molded, comprising the following components in parts by mass:

[0024]

[0025] Preferably:

[0026] 82-92 parts of polyketone;

[0027] 1-3 parts of heat stabilizer;

[0028] 1-2 parts of antioxidant;

[0029] 5-12 parts of plasticizer;

[0030] 0.5-1 part of lubricant.

[0031] The heat stabilizer is one or a mixture of two or more of cellulose, inositol, calcium stearate, hydroxyapatite, aluminum phosphate, and aluminum silicate.

[0032] The antioxidant includes a primary antioxidant and a secondary antioxidant.

[0033] The primary antioxidant is one or a mixture of two or more of 2,6-di-tert-butyl-4-methylphenol (antioxidant 264), pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (antioxidant 1010), bis(4-octylphenyl) diphosphate (antioxidant 1076), 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 1330).

[0034] The auxiliary antioxidant is one of tri-tert-butyl-p-hydroxyphenylpropane (antioxidant 168), bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626), and dioctadecyl pentaerythritol diphosphite (antioxidant 618), or a mixture of two or more thereof.

[0035] The dosage ratio of the primary antioxidant to the secondary antioxidant is 1:5 to 5:1, preferably 1:3 to 3:1.

[0036] The plasticizer is selected from one of acetyl tributyl citrate, N-butylbenzenesulfonamide, and ABS resin, or a mixture of two or more thereof.

[0037] The lubricant is selected from silicone powder, glycerin, polyethylene wax, or a mixture of two or more thereof.

[0038] A method for preparing a high molecular weight polyketone resin composite material that can be processed by injection molding comprises the following steps:

[0039] a) mixing polyketone, heat stabilizer, antioxidant, plasticizer and lubricant by solvent method to obtain a mixture;

[0040] b) melt-injection-molding and extruding the mixture to obtain a high molecular weight polyketone resin composite material.

[0041] In the step a), the solvent is dichloromethane, and the solvent is removed after mixing and stirring for 30 minutes.

[0042] In the step b), melt injection extrusion is performed using a micro-mixing rheometer and a micro-injection molding system; in the micro-mixing rheometer and the micro-injection molding system, the feeding cylinder melt temperature is 220-260° C., the mold temperature is 90-130° C., the injection pressure is 500 bar, and the holding time is 20 s.

[0043] Beneficial effects of the present invention:

[0044] (1) Using cheap and readily available bulk industrial products such as olefins and carbon monoxide as raw materials, directly prepare polyketone polymer materials with high added value and excellent performance;

[0045] (2) The high molecular weight polyketone material of the present invention can be simply and effectively prepared under mild conditions in the presence of a specific nickel catalyst.

[0046] (3) High molecular weight polyketone can achieve stable injection molding processing without damaging its intrinsic properties, providing possibilities for subsequent applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is the GPC chart of the polyketone obtained by the synthesis method provided in Example 1 of the present invention.

[0048] Figure 2 The tensile diagram of the polyketone obtained by the synthesis method provided in Example 3 of the present invention. Figure 3 The thermogram of the polyketone obtained by the synthesis method provided in Example 8 of the present invention measured by differential scanning calorimetry. Detailed implementation manners

[0049] The following further describes the detailed implementation manners of the present invention in combination with the accompanying drawings and technical solutions.

[0050] The data given in the examples include the specific process and parameters of the ternary polymerization. This polymerization process is carried out under an inert atmosphere or environment of anhydrous and anaerobic conditions. All sensitive substances are stored in a glove box or refrigerator at -30°C. All solvents are strictly dried to remove water and oxygen; unless otherwise specified, all other raw materials are used directly after purchase.

[0051] Example 1:

[0052] In a 500 mL mechanical stirring kettle, the following substances are added in sequence at room temperature: 20 μmol of phosphonic acid Ni catalyst, 100 mL of dichloromethane, and methanol (chain transfer reagent / catalyst = 200 / 1); first, a certain mass of olefins within C3 - C10 is charged, and then a mixed gas of ethylene and CO with a molar ratio of 1:1 is charged. Under the conditions of controlling the reaction pressure at 4 MPa and the heating temperature at 70 - 90°C, start stirring and carry out a constant-pressure reaction for 4 h. After reaching the set time, stop stirring, slowly release the remaining mixed gas, add methanol to quench, then add a large amount of methanol for precipitation, filter the polymer, and dry it to a constant weight under vacuum. The polymerization results are shown in Table 1 below. Gel permeation chromatography is used to measure the molecular weight and its distribution of the polymer; Varian INOVA-400MHz is used to measure its 1 HNMR to obtain the insertion rate of long-chain olefins. Differential scanning calorimetry is used to test its melting point.

[0053] Table 1. Copolymerization reaction of ethylene / carbon monoxide / α-olefin catalyzed by phosphonic acid Ni complex

[0054]

[0055] Note 1: Polymerization conditions: 20 μmol of phosphonic acid Ni catalyst, 100 mL of dichloromethane, methanol (molar ratio of chain transfer reagent / catalyst = 200 / 1), reaction temperature 80°C, ethylene / CO volume ratio = 1 / 1, reaction time 4 h, total pressure 4.0 MPa, constant-pressure reaction, 300 mL mechanical stirring kettle;

[0056] Note 2: Turnover number: g PK (g of Ni) -1 ;

[0057] Note 3: Insertion ratio of C3 - C10 in mol% ( 1 determined by 1H NMR spectrum);

[0058] Note 4: Molecular weight: kg / mol -1 , molecular weight and molecular weight distribution were determined by gel permeation chromatography at 40 °C, with hexafluoroisopropanol as the eluent;

[0059] Note 5: Melting temperature T m determined by differential scanning calorimetry (DSC), second heating, and the broad melting endothermic peak;

[0060] Note 6: The polymerization conditions for sequences 4 and 11 were 100 μmol of phosphonic acid Ni catalyst, 200 mL of dichloromethane, and a 500 mL mechanically stirred autoclave, with other conditions the same as in Note 1.

[0061] Note 7: The polymerization conditions for sequences 12 and 17 were 70 °C, with other conditions the same as in Note 1.

[0062] Note 8: The polymerization conditions for sequences 13 and 18 were 90 °C, with other conditions the same as in Note 1.

[0063] Example 2:

[0064] In a 500 mL mechanically stirred autoclave, the following substances were added in sequence at room temperature: 20 μmol of phosphonic acid Ni catalyst, 100 mL of dichloromethane, and methanol (chain transfer agent / catalyst = 200 / 1); first, a certain mass of olefins within C3 - C10 was charged, and then a mixture of ethylene and CO with a molar ratio of 1:1 was charged. Under the conditions of controlling the reaction pressure at 4 MPa and the heating temperature at 80 °C, stirring was started, and the reaction was carried out at a constant pressure for 0.5 - 8 h. After reaching the set time, stirring was stopped, the remaining mixture gas was slowly released, methanol was added to quench, and then a large amount of methanol was added for precipitation. The polymer was filtered and dried to a constant weight under vacuum. The polymerization results are shown in Table 2 below. Gel permeation chromatography was used to determine the molecular weight and its distribution of the polymer; Varian INOVA - 400 MHz was used to determine its 1 1H NMR to obtain the insertion rate of long - chain olefins. Differential scanning calorimetry was used to test its melting point.

[0065] Table 2. Influence of different reaction times on the polymerization reaction

[0066]

[0067]

[0068] Note 1: Polymerization conditions: 20 μmol phosphinosulfonic acid Ni catalyst, 100 mL dichloromethane, methanol (chain transfer reagent / catalyst molar ratio = 200 / 1), reaction temperature 80 °C, ethylene / CO volume ratio = 1 / 1, 90 g of 1-hexene charged, 100 g of 1-octene charged, total pressure 4.0 MPa, constant pressure reaction, 300 mL mechanical stirring autoclave;

[0069] Note 2: Turnover number: g PK (g of Ni) -1 ;

[0070] Note 3: C3-C10 insertion ratio mol% ( 1 determined by 1H NMR spectrum);

[0071] Note 4: Molecular weight: kg mol -1 , the molecular weight and molecular weight distribution were determined by gel permeation chromatography at 40 °C, with hexafluoroisopropanol as the eluent;

[0072] Note 5: Melting temperature T m determined by differential scanning calorimetry (DSC), second heating, with a broad melting endothermic peak;

[0073] Example 3:

[0074] 40 g of polyketone resin obtained by polymerization (inserted with propylene, molecular weight 282 kg mol -1 , melting point 234 °C), 800 mg of hydroxyapatite, 400 mg of primary antioxidant 1010, 200 mg of secondary antioxidant 168, 6 g of tributyl acetylcitrate, 80 mg of silicone powder, were mixed evenly by the solvent method and then placed in a constant temperature and humidity drying oven at 80 °C for 6 h to obtain a mixed material.

[0075] Example 4:

[0076] 40 g of polyketone resin obtained by polymerization (inserted with propylene, molecular weight 245 kg mol -1 , melting point 219 °C), 200 mg of aluminum phosphate, 200 mg of primary antioxidant 1330, 200 mg of secondary antioxidant 618, 2 g of N-butylbenzenesulfonamide, 40 mg of polyethylene wax, were mixed evenly by the solvent method and then placed in a constant temperature and humidity drying oven at 80 °C for 6 h to obtain a mixed material.

[0077] Example 5:

[0078] 40 g of polyketone resin obtained by polymerization (inserted with 1-butene, molecular weight 272 kg mol -1, 400 mg of aluminum silicate, 100 mg of primary antioxidant 1076, 200 mg of secondary antioxidant 168, 4 g of ABS resin, 120 mg of glycerol. After mixing evenly by the solvent method, it was placed in a constant temperature and humidity drying oven and dried at 80 °C for 6 h to obtain a mixed material.

[0079] Example 6:

[0080] 40 g of polyketone resin obtained by polymerization (inserting 1-butene, molecular weight 239 kg / mol -1 , melting point 218 °C), 500 mg of calcium stearate, 300 mg of primary antioxidant 264, 100 mg of secondary antioxidant 168, 8 g of tributyl acetylcitrate, 100 mg of polyethylene wax. After mixing evenly by the solvent method, it was placed in a constant temperature and humidity drying oven and dried at 80 °C for 6 h to obtain a mixed material.

[0081] Example 7:

[0082] 40 g of polyketone resin obtained by polymerization (inserting 1-hexene, molecular weight 276 kg / mol -1 , melting point 236 °C), 900 mg of aluminum silicate, 400 mg of primary antioxidant 1076, 200 mg of secondary antioxidant 618, 6 g of N-butylbenzenesulfonamide, 360 mg of glycerol. After mixing evenly by the solvent method, it was placed in a constant temperature and humidity drying oven and dried at 80 °C for 6 h to obtain a mixed material.

[0083] Example 8:

[0084] 40 g of polyketone resin obtained by polymerization (inserting 1-hexene, molecular weight 228 kg / mol -1 , melting point 232 °C), 300 mg of aluminum phosphate, 200 mg of primary antioxidant 1010, 400 mg of secondary antioxidant 626, 4 g of tributyl acetylcitrate, 240 mg of silicone powder. After mixing evenly by the solvent method, it was placed in a constant temperature and humidity drying oven and dried at 80 °C for 6 h to obtain a mixed material.

[0085] Example 9:

[0086] 40 g of polyketone resin obtained by polymerization (inserting 1-hexene, molecular weight 217 kg / mol -1 , melting point 233 °C), 600 mg of cellulose, 300 mg of primary antioxidant 264, 100 mg of secondary antioxidant 168, 2 g of ABS resin, 200 mg of glycerol. After mixing evenly by the solvent method, it was placed in a constant temperature and humidity drying oven and dried at 80 °C for 6 h to obtain a mixed material.

[0087] Example 10:

[0088] 40 g of the polymerized polyketone resin (inserted with 1-octene, molecular weight 299 kg / mol -1 , melting point 250 °C), 1 g of hydroxyapatite, 400 mg of primary antioxidant 1076, 100 mg of secondary antioxidant 168, 6 g of N-butylbenzenesulfonamide, 300 mg of polyethylene wax were uniformly mixed using the solvent method and then placed in a constant temperature and humidity drying oven at 80 °C for 6 h to obtain a mixed material.

[0089] Example 11:

[0090] 40 g of the polymerized polyketone resin (inserted with 1-octene, molecular weight 237 kg / mol -1 , melting point 244 °C), 1 g of calcium stearate, 200 mg of primary antioxidant 264, 400 mg of secondary antioxidant 626, 4 g of ABS resin, 300 mg of glycerol were uniformly mixed using the solvent method and then placed in a constant temperature and humidity drying oven at 80 °C for 6 h to obtain a mixed material.

[0091] Example 12:

[0092] 40 g of the polymerized polyketone resin (inserted with 1-decene, molecular weight 269 kg / mol -1 , melting point 247 °C), 2 g of inositol, 400 mg of primary antioxidant 1330, 400 mg of secondary antioxidant 618, 8 g of tributyl acetylcitrate, 400 mg of silicone powder were uniformly mixed using the solvent method and then placed in a constant temperature and humidity drying oven at 80 °C for 6 h to obtain a mixed material.

[0093] The materials obtained in Examples 3 to 12 were subjected to various performance tests, and the results are shown in Table 3.

[0094] Physical and mechanical properties: Various physical and mechanical property tests were carried out on the processed products. The tensile property test was carried out with reference to the GB / T 1040.2-2006 standard, and the tensile rate was 10 mm / min.

[0095] The yellowness test was carried out using a spectrophotometer, Hunterlab UltraScan Pro, in the RSEX - removing specular reflection mode. The test wavelength was 350 - 1050 nm CIE visible light and near-infrared light, the sampling interval was 5 nm, and the photometric range was 0 - 150%.

[0096] Table 3. Performance test results of the products obtained in Examples 3 to 12

[0097]

Claims

1. A method for preparing a high molecular weight polyketone resin that can be injection molded, characterized in that: The synthetic route of high molecular weight polyketone resin is as follows: The steps are as follows: in a glove box, a nickel catalyst and a chain transfer agent are dissolved in a solvent to obtain a uniform solution; the obtained solution is transferred to a mechanical stirring kettle through a feeding tank, stirring is started, olefins within C3 to C10 are introduced, and after the temperature rises to a required temperature, a mixed gas of ethylene and carbon monoxide with a volume ratio of 1:1 at a certain pressure is charged into the mechanical stirring kettle, the reaction kettle is cooled after the reaction is completed, and the remaining gas in the mechanical stirring kettle is released after it returns to room temperature, and a methanol solvent is added to quench the polymerization reaction, and a polyketone resin is obtained after filtering and drying; The catalyst structure used is shown below: The structure of polyketone resin is shown below: Wherein, R is an olefin within the range of C3 to C10, including propylene, 1-butene, 1-hexene, 1-octene, and 1-decene; The molecular weight of the polyketone is between 200 and 400 kg / mol, the molecular weight distribution is between 1.5 and 3.0, and the melting point is between 200 and 250°C.

2. The preparation method according to claim 1, characterized in that: The chain transfer agent is one or a mixture of two or more of methanol, tert-butyl alcohol, propylene glycol, benzyl alcohol, hydrogen, lithium triisobutylborohydride, and sodium trimethoxyborohydride, and the molar ratio of the chain transfer agent to the nickel catalyst is (10-1000):

1.

3. The preparation method according to claim 1, characterized in that: The reaction temperature in the mechanical stirring kettle is 70-130° C., the reaction pressure is 1-6 MPa, the reaction time is 0.5-12 h, and the stirring speed is 100-800 r / min.

4. The preparation method according to claim 1, characterized in that: The molar ratio of C3-C10 olefins to carbon monoxide used in the reaction in the mechanically stirred kettle is (1-100):

1.

5. The preparation method according to claim 1, characterized in that: The solvent is one or a mixture of two or more of toluene, dichloromethane, methanol, methyl tert-butyl ether, chlorobenzene, n-hexane, cyclohexane, and tetrahydrofuran, and the concentration of the nickel catalyst is 0.1 to 1 mmol L -1 .

6. A composite material of a high molecular weight polyketone resin obtained by the preparation method according to claims 1-5, characterized in that: The composite material comprises the following components in parts by weight:

7. The composite material according to claim 6, characterized in that The composite material comprises the following components in parts by weight:

8. The composite material according to claim 6, characterized in that The heat stabilizer is one or a mixture of two or more of cellulose, inositol, calcium stearate, hydroxyapatite, aluminum phosphate and aluminum silicate; The antioxidant includes a primary antioxidant and a secondary antioxidant, and the dosage ratio of the primary antioxidant and the secondary antioxidant is 1:5 to 5:1; The main antioxidant is one or a mixture of two or more of 2,6-di-tert-butyl-4-methylphenol (antioxidant 264), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis(4-octylphenol) diphosphate, and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; The auxiliary antioxidant is one or a mixture of two or more of tri-tert-butyl-p-hydroxyphenylpropane, bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite, and dioctadecyl pentaerythritol diphosphite; The plasticizer is selected from one or a mixture of two or more of acetyl tributyl citrate, N-butylbenzenesulfonamide, and ABS resin; The lubricant is selected from silicone powder, glycerin, polyethylene wax, or a mixture of two or more thereof.

9. A method for preparing a composite material of a high molecular weight polyketone resin according to claim 6, characterized in that: The following steps are involved: a) mixing polyketone, heat stabilizer, antioxidant, plasticizer and lubricant by solvent method to obtain a mixture; b) melt-injection-molding and extruding the mixture to obtain a high molecular weight polyketone resin composite material.

10. The preparation method according to claim 9, characterized in that: In step a), the solvent is dichloromethane, and the solvent is removed after mixing and stirring for 30 minutes; In step b), melt injection extrusion is performed using a micro-mixing rheometer and a micro-injection molding system; in the micro-mixing rheometer and the micro-injection molding system, the feeding cylinder melt temperature is 220-260° C., the mold temperature is 90-130° C., the injection pressure is 500 bar, and the holding time is 20 s.

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