Antibacterial and antistatic modified PP material and preparation method thereof

Abstract

The present application relates to a kind of antibacterial antistatic modified PP material and its preparation method, belong to polymer material technical field.The present application is first prepared modified halloysite: halloysite nanotube is loaded with composite essential oil, after being plugged by carboxylated calabash [6] urea port inclusion, epoxy group is grafted;With cashphenol as core, it is prepared by partial esterification end-capping with synthetic ionic liquid after polycondensation and ionic liquid.Especially, ionic liquid residual hydroxyl, carboxyl and modified halloysite, PP-g-GMA open loop grafting during melt extrusion process.The present application realizes low humidity antistatic by ionic conduction and nanochannel auxiliary, combines slow-release-contact dual antibacterial mechanism, synergizes free radical capture and lamellar barrier effect, and gives material excellent antistatic, antibacterial and heat and oxygen aging resistance performance.Modified PP material prepared by the present application has the effects of antistatic, antibacterial and heat and oxygen aging resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an antibacterial and antistatic modified PP material and its preparation method. Background Technology

[0002] Polypropylene (PP) is widely used in home appliances, packaging, and other fields due to its excellent processability and low cost. However, its intrinsic insulation properties easily lead to static electricity accumulation, its surface is prone to bacterial growth, and its molecular chains are easily aged and degraded in hot and oxidative environments, severely limiting its high-value applications. Existing PP modification technologies have significant limitations: conventional antistatic agents depend on ambient humidity, and their antistatic effect drops sharply in low humidity; small-molecule antibacterial agents are prone to migration and precipitation, resulting in short antibacterial duration and safety risks; single antioxidants or nanofillers cannot simultaneously achieve synergistic effects of antistatic, antibacterial, and aging resistance. Nanofillers such as halloysite suffer from poor dispersibility and limited functionality, while modification with ordinary ionic liquids is prone to insufficient compatibility and precipitation, failing to achieve long-term functional stability. Therefore, developing PP functional modification technologies that offer synergistic multi-performance, low-humidity adaptability, and long-term stability is a key requirement for expanding its high-end application scenarios. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial and antistatic modified PP material and its preparation method, so as to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing an antibacterial and antistatic modified PP material, comprising the following steps: (1) Halloysite nanotubes were dispersed in water, sonicated, centrifuged and activated with hydrochloric acid to obtain activated halloysite; composite antibacterial essential oil was vacuum loaded onto activated halloysite, washed with ethanol and dried to obtain halloysite nanotubes loaded with essential oil; cucurbit[6]urea and deionized water were mixed at a mass ratio of 1:200, and potassium persulfate of 5 to 7 times the mass of cucurbit[6]urea was added under stirring at 85°C and reacted for 24 h, and the product was obtained by methanol precipitation and gel chromatography desalting to obtain the all-hydroxy product; then, the product was successively subjected to methanesulfonyl chloride esterification, sodium cyanide cyanation and hydrochloric acid hydrolysis carboxylation to obtain the all-carboxylated cucurbit[6]urea; halloysite loaded with essential oil was dispersed in buffer solution, and all-carboxylated cucurbit[6]urea of ​​0.05 to 0.15 times the mass of halloysite loaded with essential oil was added, and the product was covalently capped by activating agent and modified with silane to obtain the self-made modified halloysite; (2) Cashew phenol, dimethylolpropionic acid and catalyst were mixed at a mass ratio of 1:1~1.5:0.01 and reacted under reduced pressure under nitrogen protection at 140°C. Trimethylolpropane with a mass of 0.35 times that of cashew phenol was added and the reaction was continued for 2 hours. After organic dissolution, hexane precipitation and drying, cashew phenol derivative was obtained. It was mixed with ionic liquid precursor and reacted at 25°C for 48 hours. After precipitation and dialyzing for 48 hours, the self-made ionic liquid was obtained by freeze drying. (3) 90-110 parts by weight of homopolymer polypropylene resin, 4-6 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant A, 0.3 parts by weight of antioxidant B, 0.5 parts by weight of calcium stearate, 5-15 parts by weight of self-made ionic liquid, and 3-8 parts by weight of self-made modified halloysite nanotubes are mixed and then extruded, injection molded and annealed to obtain antibacterial and antistatic modified PP material.

[0005] 2. The antibacterial and antistatic modified PP material according to claim 1, characterized in that the halloysite nanotubes in step (1) have: an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m². 2 / g.

[0006] 3. The antibacterial and antistatic modified PP material according to claim 1, characterized in that the composite antibacterial essential oil in step (1) is prepared by mixing eugenol and thymol in a mass ratio of 1:1.

[0007] 4. The antibacterial and antistatic modified PP material according to claim 1, characterized in that the activating agent in step (1) is a mixed solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in an amount 0.8 times the mass of total carboxylated cucurbit[6]urea and N-hydroxysuccinimide in an amount 0.5 times the mass of total carboxylated cucurbit[6]urea.

[0008] 5. The antibacterial and antistatic modified PP material according to claim 1, wherein the silane in step (1) is KH-560.

[0009] 6. The antibacterial and antistatic modified PP material according to claim 1, wherein the catalyst in step (2) is p-toluenesulfonic acid.

[0010] 7. The antibacterial and antistatic modified PP material according to claim 1, characterized in that the ionic liquid precursor in step (2) is: 1-carboxyethyl-3-methylimidazolium tetrafluoroborate.

[0011] 8. The antibacterial and antistatic modified PP material according to claim 1, characterized in that the homopolymer polypropylene resin in step (3) has a melt flow rate of 15 g / 10 min.

[0012] 9. The antibacterial and antistatic modified PP material according to claim 1, wherein the antioxidant A in step (3) is antioxidant 1010.

[0013] 10. The antibacterial and antistatic modified PP material according to claim 1, wherein the antioxidant B in step (3) is antioxidant 168.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: This invention prepares antibacterial and antistatic modified PP material by mixing self-made modified halloysite with self-made ionic liquid PP material monomer components, so as to achieve antibacterial, antistatic and long-term stable effects.

[0015] This invention first loads halloysite nanotubes with thymol / eugenol composite essential oil via vacuum suction, and then uses carboxylated cucurbita[6]urea to perform supramolecular encapsulation and sealing at the tube ends. The surface is then modified with KH-560 and grafted with epoxy groups to obtain self-made modified halloysite. Secondly, using biomass cashew phenol as the core, a self-made ionic liquid is obtained by polycondensation with dimethylolpropionic acid and partial esterification and end-capping with 1-carboxyethyl-3-methylimidazolium tetrafluoroborate. During the melt extrusion process, the residual hydroxyl and carboxyl groups of the self-made ionic liquid simultaneously undergo ring-opening with the modified halloysite and PP-g-GMA to obtain antibacterial and antistatic modified P P material; the self-made ionic liquid imidazole cation-tetrafluoroborate ion pair constructs an efficient ion conduction pathway, and halloysite nanochannels bind trace amounts of moisture to assist ion hopping transport. The synergy of these two factors enables the material to maintain excellent antistatic properties even under low humidity. The slow-release and long-lasting bactericidal effect of cucurbitacin-terminated plant essential oil and the contact-based rapid bactericidal effect of the ionic liquid imidazole salt form a slow-release and contact-based antibacterial mechanism, endowing the material with excellent antibacterial properties. At the same time, the free radical scavenging and antioxidant capacity endowed by the cashew phenolic structure and the labyrinth barrier effect of the halloysite layers work synergistically to significantly improve the long-term heat and oxygen aging stability of the material. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The testing methods for various indicators of the modified PP material prepared in the following embodiments are as follows: Antibacterial performance test: The modified polypropylene materials prepared in Examples 1-5 and Comparative Examples 1-6 were tested according to GB / T 31402-2015 "Test Method for Antibacterial Performance of Plastic Surfaces".

[0018] Antistatic performance test: The modified polypropylene materials prepared in Examples 1-5 and Comparative Examples 1-6 were tested according to GB / T 1410-2006 "Test methods for volume resistivity and surface resistivity of solid insulating materials".

[0019] Heat and oxygen aging resistance test: The modified polypropylene materials prepared in Examples 1-5 and Comparative Examples 1-6 were tested according to GB / T 7141-2008 "Test Method for Heat Aging of Plastics". Example 1

[0020] (1) Halloysite nanotubes with an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m² / g were dispersed in deionized water at a solid-liquid mass ratio of 1:20. The mixture was sonicated at 20 kHz for 30 min, allowed to stand for 24 h, and then the upper suspension was centrifuged at 3000 rpm for 15 min. The precipitate was collected, dried at 80 °C under vacuum of -0.09 MPa for 12 h, ground through a 200-mesh sieve, and 3 mol / L hydrochloric acid was added at a solid-liquid mass ratio of 1:20. The mixture was stirred at 60 °C for 4 h, washed with deionized water until neutral, and dried under vacuum at 80 °C for 12 h to obtain activated halloysite nanotubes. Eugenol and thymol were mixed at a mass ratio of 1:1 to obtain a composite antibacterial essential oil. The activated halloysite nanotubes were placed in a double-necked flask, and the vacuum was drawn to -0.095 MPa and maintained for 30 min. The composite essential oil was slowly injected under vacuum, and the mass ratio of the essential oil to the activated halloysite nanotubes was controlled to be 1:1. Return to normal pressure, stir at 25℃ and 200 rpm for 12 h. Quickly rinse the surface once with anhydrous ethanol, and dry at 30℃ for 2 h to obtain halloysite nanotubes loaded with essential oil; (2) Cucurbita[6]urea and deionized water were mixed at a mass ratio of 1:200, heated to 85°C and stirred vigorously to suspend cucurbita[6]urea evenly. Then, potassium persulfate was added at a mass ratio of 5 times that of cucurbita[6]urea within 30 min, and the reaction was continued at 85°C for 24 h. After cooling to room temperature, an equal volume of methanol was added, and the mixture was concentrated under reduced pressure to about 50 mL. Then, 200 mL of methanol was added again to precipitate the precipitate. The precipitate was filtered and washed three times with methanol. The crude product was dissolved in a small amount of water, washed with water to remove desalting via gel chromatography, and the first elution peak was collected, concentrated, and freeze-dried to obtain the all-hydroxyl product. Anhydrous N,N-dimethylformamide was mixed at a mass ratio of 1:10 and stirred until completely dissolved. Anhydrous triethylamine, twice the mass of the hydroxyl product, was added as an acid-binding agent. The mixture was cooled to 0°C in an ice bath under nitrogen protection. Methanesulfonyl chloride, 1.5 times the mass of the hydroxyl product, was dissolved in anhydrous dichloromethane at a solid-liquid ratio of 1:4 and slowly added dropwise to the reaction solution over 1 hour. The mixture was stirred at 0°C for 2 hours, then the temperature was raised to 25°C and the reaction continued for 24 hours. The resulting triethylamine hydrochloride precipitate was filtered off. The filtrate was concentrated under reduced pressure to 1 / 3 of its original volume and slowly poured into 1 L of ice-cold diethyl ether to precipitate the precipitate. After filtration, the precipitate was washed three times with anhydrous diethyl ether and then cooled at 40°C. The product was dried for 12 hours to obtain the full methanesulfonate product. The full methanesulfonate product was then mixed with anhydrous dimethyl sulfoxide at a mass ratio of 1:15 and stirred until dissolved. Sodium cyanide at 0.3 times the mass of the full methanesulfonate product was added. The mixture was reacted at 70°C under nitrogen protection, stirred at 300 rpm for 48 hours. After cooling to room temperature, the insoluble matter was filtered off. The filtrate was slowly poured into 1 L of ice-cold ether to precipitate the product. The precipitate was dissolved in 50 mL of deionized water and dialyzed against deionized water for 48 hours, changing the water every 6 hours to remove salts. The product was then freeze-dried to obtain the full cyano product. Finally, the full cyano product... The substance was mixed with 6 mol / L hydrochloric acid at a mass ratio of 1:20 and stirred to disperse. The reaction was carried out at 100℃ for 24 h to complete the cyano hydrolysis. After cooling to room temperature, the precipitate was centrifuged at 5000 rpm for 10 min. The precipitate was washed three times with deionized water. The precipitate was dissolved in a small amount of 0.1 mol / L sodium hydroxide solution to dissolve the carboxyl group. The precipitate was washed with water and desalted by Sephadex G-25 gel chromatography column and the first elution peak was collected. The pH of the eluent was adjusted to 2 with 0.1 mol / L hydrochloric acid to ionize the carboxyl group and precipitate. After centrifugation and collection, the precipitate was washed with water until neutral and then freeze-dried to obtain the all-carboxylated cucurbita[6]urea. (3) Disperse halloysite nanotubes loaded with essential oil in an acetate-sodium acetate buffer solution at pH=5 with a solid content of 1wt%. Disperse the nanotubes at 20kHz for 2h to fully deagglomerate and expose the ends to obtain a suspension. Dissolve all-carboxylated cucurbita[6]urea in an equal mass of an acetate-sodium acetate buffer solution at pH=5. Control the mass ratio of all-carboxylated cucurbita[6]urea to halloysite nanotubes loaded with essential oil to be 0.5:10. Slowly drip the all-carboxylated cucurbita[6]urea solution into the suspension. Stir the reaction at 25℃ for 12h to achieve selective end-capping. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added sequentially to the reaction solution. The amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.8 times the mass of the all-carboxylated cucurbit[6]urea, and the amount of N-hydroxysuccinimide was 0.5 times the mass of the all-carboxylated cucurbit[6]urea. The reaction was stirred at 300 rpm for 6 h at 25 °C to form a covalent ester bond between the carboxyl group of the all-carboxylated cucurbit[6]urea and the Al-OH of the halloysite nanotube port, thus achieving permanent covalent end-capping. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min and washed three times with deionized water to obtain the intermediate product. The intermediate product was dispersed in a mixed solvent of toluene / water at a volume ratio of 95:5, with a solid content of 2 wt%. KH-560 was added, and the mass ratio of KH-560 to the intermediate product was controlled at 0.3:1. The reaction was stirred at 70 °C for 6 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min, washed twice with anhydrous toluene and twice with anhydrous ethanol, and dried under vacuum at 60℃ for 6 h to obtain the self-made modified halloysite. (4) Cashew nut phenol, dimethylolpropionic acid and p-toluenesulfonic acid catalyst were mixed in a mass ratio of 1:1:0.01, stirred at 140°C under nitrogen protection, and depressurized to -0.08 MPa to remove water. When the acid value dropped to 60% of the initial value, 0.35 times the mass of cashew nut phenol trimethylolpropane was added, and the reaction was continued for 2 hours. The product was dissolved in tetrahydrofuran, and the amount used was 5 times the mass of the crude product. It was precipitated twice in n-hexane, and the volume ratio of the solution to n-hexane was 1:5. The cashew nut phenol derivative was obtained by vacuum drying at 60°C. The cashew nut phenol derivative, 1-carboxyethyl-3-methylimidazolium tetrafluoroborate, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine were added to the reaction flask in a mass ratio of 1:0.4:0.4:0.02. Anhydrous N,N-dimethylformamide was added to make the total solid content 20 wt%. The reaction was stirred at 25°C under nitrogen protection for 48 hours. The precipitate was filtered off, and the filtrate was concentrated to one-quarter of the original volume under reduced pressure at 50°C. The concentrate was slowly added dropwise to anhydrous diethyl ether with vigorous stirring at 2000 rpm, at a volume ratio of 1:5. A precipitate formed, and after standing, the supernatant was discarded. This ether precipitation process was repeated three times. The final precipitate was mixed with deionized water at a mass ratio of 1:5 and placed in a dialysis bag with a molecular weight cutoff of 1000 Da. Dialysis was performed in deionized water for 48 hours, with the dialysis fluid replaced every 6 hours. The mixture was then freeze-dried at -50°C for 48 hours to obtain the self-made ionic liquid. (5) 90 parts by weight of homopolymer polypropylene resin with a melt flow rate of 15 g / 10 min, 4 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of calcium stearate were mixed at 500 rpm for 3 min; the speed was reduced to 200 rpm, 5 parts by weight of self-made ionic liquid were added, and the mixture was continued for 2 min; then 3 parts by weight of self-made modified halloysite nanotubes were added and mixed for 3 min to obtain a premix. The premix was fed into a co-rotating twin-screw extruder, and the temperatures of each section from the feeding section to the die head were set to 160℃, 170℃, 180℃, 190℃, 195℃, 195℃, and 190℃ respectively, the screw speed was 200 rpm, the feed rate was 3 kg / h, and a vacuum of -0.08 MPa was applied to the penultimate section to remove volatiles. After being cooled in a water bath and air-dried, the extrudate was cut into 3mm pellets by a rotary pelletizer and then molded into standard test specimens using an injection molding machine. The injection molding machine barrel temperature was set to 180-190-200-195℃, the mold temperature to 50℃, the injection pressure to 70MPa, the holding time to 13s, and the cooling time to 25s. The injection-molded specimens were annealed in an 80℃ oven for 2 hours and then slowly cooled to room temperature to further complete the dynamic covalent crosslinking reaction and eliminate internal stress, thus obtaining an antibacterial and antistatic modified polypropylene material. Example 2

[0021] (1) Halloysite nanotubes with an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m² / g were dispersed in deionized water at a solid-liquid mass ratio of 1.2:20. The mixture was sonicated at 20 kHz for 30 min, allowed to stand for 24 h, and then the upper suspension was centrifuged at 3000 rpm for 15 min. The precipitate was collected, dried at 80 °C under vacuum of -0.09 MPa for 12 h, ground through a 200-mesh sieve, and 3 mol / L hydrochloric acid was added at a solid-liquid mass ratio of 1:20. The mixture was stirred at 60 °C for 4 h, washed with deionized water until neutral, and dried under vacuum at 80 °C for 12 h to obtain activated halloysite nanotubes. Eugenol and thymol were mixed at a mass ratio of 1:1 to obtain a composite antibacterial essential oil. The activated halloysite nanotubes were placed in a double-necked flask, and the vacuum was drawn to -0.095 MPa and maintained for 30 min. The composite essential oil was slowly injected under vacuum, and the mass ratio of the essential oil to the activated halloysite nanotubes was controlled to be 1:1.5. Return to normal pressure, stir at 25℃ and 200 rpm for 12 h. Quickly rinse the surface once with anhydrous ethanol, and dry at 30℃ for 2 h to obtain halloysite nanotubes loaded with essential oil; (2) Cucurbita[6]urea and deionized water were mixed at a mass ratio of 1:200, heated to 85°C and stirred vigorously to suspend cucurbita[6]urea evenly. Then, potassium persulfate of 5.5 times the mass of cucurbita[6]urea was added within 30 min, and the reaction was continued at 85°C for 24 h. After cooling to room temperature, an equal volume of methanol was added, and the mixture was concentrated under reduced pressure to about 50 mL. Then, 200 mL of methanol was added again to precipitate the precipitate. The precipitate was filtered and washed three times with methanol. The crude product was dissolved in a small amount of water, washed with water to remove desalting via gel chromatography, and the first elution peak was collected, concentrated, and freeze-dried to obtain the all-hydroxyl product. The product was mixed with anhydrous N,N-dimethylformamide at a mass ratio of 1.2:10 and stirred until completely dissolved. Anhydrous triethylamine, twice the mass of the hydroxyl product, was added as an acid-binding agent. The mixture was cooled to 0°C in an ice bath under nitrogen protection. Methanesulfonyl chloride, 1.5 times the mass of the hydroxyl product, was dissolved in anhydrous dichloromethane at a solid-liquid ratio of 1:4 and slowly added dropwise to the reaction solution over 1 hour. The mixture was stirred at 0°C for 2 hours, then the temperature was raised to 25°C and the reaction continued for 24 hours. The resulting triethylamine hydrochloride precipitate was filtered off. The filtrate was concentrated under reduced pressure to 1 / 3 of its original volume and slowly poured into 1 L of ice-cold diethyl ether to precipitate the precipitate. After filtration, the precipitate was washed three times with anhydrous diethyl ether. The product was dried at 0℃ for 12 h to obtain the full methanesulfonate product. The full methanesulfonate product was mixed with anhydrous dimethyl sulfoxide at a mass ratio of 1:15 and stirred until dissolved. Sodium cyanide at 0.3 times the mass of the full methanesulfonate product was added. The mixture was reacted at 70℃ in the dark under nitrogen protection with stirring at 300 rpm for 48 h. After cooling to room temperature, the insoluble matter was filtered off. The filtrate was slowly poured into 1 L of ice-cold diethyl ether to precipitate the product. After filtration, the precipitate was dissolved in 50 mL of deionized water and dialyzed against deionized water for 48 h, changing the water every 6 h to remove salts. The product was then freeze-dried to obtain the full cyano product. Finally, the full cyano product was... The product was mixed with 6 mol / L hydrochloric acid at a mass ratio of 1:20 and stirred to disperse. The reaction was carried out at 100℃ for 24 h to complete the cyano hydrolysis. After cooling to room temperature, the product was centrifuged at 5000 rpm for 10 min. The precipitate was washed three times with deionized water. The precipitate was dissolved in a small amount of 0.1 mol / L sodium hydroxide solution to dissolve the carboxyl group. The product was washed with water and desalted by Sephadex G-25 gel chromatography column and the first elution peak was collected. The pH of the eluent was adjusted to 2 with 0.1 mol / L hydrochloric acid to ionize the carboxyl group and precipitate. After centrifugation and collection, the product was washed with water until neutral and then freeze-dried to obtain the all-carboxylated cucurbita[6]urea. (3) Disperse halloysite nanotubes loaded with essential oil in an acetate-sodium acetate buffer solution at pH=5 with a solid content of 1.5wt%. Disperse the nanotubes by ultrasonication at 20kHz for 2h to fully deagglomerate and expose the ends to obtain a suspension. Dissolve all-carboxylated cucurbita[6]urea in an equal mass of an acetate-sodium acetate buffer solution at pH=5. Control the mass ratio of all-carboxylated cucurbita[6]urea to halloysite nanotubes loaded with essential oil to be 0.8:10. Slowly drip the all-carboxylated cucurbita[6]urea solution into the suspension. Stir the reaction at 25℃ for 12h to achieve selective end-capping. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added sequentially to the reaction solution. The amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.8 times the mass of the all-carboxylated cucurbit[6]urea, and the amount of N-hydroxysuccinimide was 0.5 times the mass of the all-carboxylated cucurbit[6]urea. The reaction was stirred at 300 rpm for 6 h at 25 °C to form a covalent ester bond between the carboxyl group of the all-carboxylated cucurbit[6]urea and the Al-OH of the halloysite nanotube port, thus achieving permanent covalent end-capping. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min and washed three times with deionized water to obtain the intermediate product. The intermediate product was dispersed in a mixed solvent of toluene / water at a volume ratio of 95:5, with a solid content of 2 wt%. KH-560 was added, and the mass ratio of KH-560 to the intermediate product was controlled at 0.3:1. The reaction was stirred at 70 °C for 6 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min, washed twice with anhydrous toluene and twice with anhydrous ethanol, and dried under vacuum at 60℃ for 6 h to obtain the self-made modified halloysite. (4) Mix cashew phenol, dimethylolpropionic acid and p-toluenesulfonic acid catalyst in a mass ratio of 1:1.1:0.01, stir at 140°C under nitrogen protection, and reduce pressure to -0.08MPa to remove water. When the acid value dropped to 60% of the initial value, 0.35 times the mass of cashew phenol in trimethylolpropane was added, and the reaction continued for 2 hours. The product was dissolved in tetrahydrofuran, with an amount 5 times the mass of the crude product. The product was precipitated twice in n-hexane, and the volume ratio of the solution to n-hexane was 1:5. The cashew phenol derivative was obtained by vacuum drying at 60°C. The cashew phenol derivative, 1-carboxyethyl-3-methylimidazolium tetrafluoroborate, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were added to a reaction flask in a mass ratio of 1:0.4:0.4:0.02. Anhydrous N,N-dimethylformamide was added to make the total solid content 20 wt%. The reaction was carried out under nitrogen protection at 25°C with stirring for 48 hours. The precipitate was filtered off, and the filtrate was concentrated under reduced pressure at 50°C to one-quarter of the original volume. The concentrate was slowly added dropwise to anhydrous diethyl ether with vigorous stirring at 2000 rpm, at a volume ratio of 1:5. A precipitate formed, and after standing, the supernatant was discarded. This ether precipitation process was repeated three times. The final precipitate was mixed with deionized water at a mass ratio of 1:5 and placed in a dialysis bag with a molecular weight cutoff of 1000 Da. Dialysis was performed in deionized water for 48 hours, with the dialysis fluid replaced every 6 hours. The mixture was then freeze-dried at -50°C for 48 hours to obtain the self-made ionic liquid. (5) 95 parts by weight of homopolymer polypropylene resin with a melt flow rate of 15 g / 10 min, 4.5 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of calcium stearate were mixed at 500 rpm for 3 min; the speed was reduced to 200 rpm, 8 parts by weight of self-made ionic liquid were added, and the mixture was continued for 2 min; then 4 parts by weight of self-made modified halloysite nanotubes were added and mixed for 3 min to obtain a premix. The premix was fed into a co-rotating twin-screw extruder, and the temperatures of each section from the feeding section to the die head were set to 160℃, 170℃, 180℃, 190℃, 195℃, 195℃, and 190℃ respectively, the screw speed was 200 rpm, the feed rate was 3 kg / h, and a vacuum of -0.08 MPa was applied to the penultimate section to remove volatiles. After being cooled in a water bath and air-dried, the extrudate was cut into 3.5mm pellets by a rotary pelletizer and then molded into standard test specimens using an injection molding machine. The injection molding machine barrel temperature was set to 180-190-200-195℃, the mold temperature to 50℃, the injection pressure to 70MPa, the holding time to 13s, and the cooling time to 25s. The injection-molded specimens were annealed in an 80℃ oven for 2 hours and then slowly cooled to room temperature to further complete the dynamic covalent crosslinking reaction and eliminate internal stress, thus obtaining an antibacterial and antistatic modified polypropylene material. Example 3

[0022] (1) Halloysite nanotubes with an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m² / g were dispersed in deionized water at a solid-liquid mass ratio of 1.5:20. The mixture was sonicated at 20 kHz for 30 min, allowed to stand for 24 h, and then the upper suspension was centrifuged at 3000 rpm for 15 min. The precipitate was collected, dried at 80 °C under vacuum of -0.09 MPa for 12 h, ground through a 200-mesh sieve, and 3 mol / L hydrochloric acid was added at a solid-liquid mass ratio of 1:20. The mixture was stirred at 60 °C for 4 h, washed with deionized water until neutral, and dried under vacuum at 80 °C for 12 h to obtain activated halloysite nanotubes. Eugenol and thymol were mixed at a mass ratio of 1:1 to obtain a composite antibacterial essential oil. The activated halloysite nanotubes were placed in a double-necked flask, and the vacuum was drawn to -0.095 MPa and maintained for 30 min. The composite essential oil was slowly injected under vacuum, and the mass ratio of the essential oil to the activated halloysite nanotubes was controlled at 1:2. Return to normal pressure, stir at 25℃ and 200 rpm for 12 h. Quickly rinse the surface once with anhydrous ethanol, and dry at 30℃ for 2 h to obtain halloysite nanotubes loaded with essential oil; (2) Cucurbita[6]urea and deionized water were mixed at a mass ratio of 1:200, heated to 85°C and stirred vigorously to suspend cucurbita[6]urea evenly. Potassium persulfate, which was 6 times the mass of cucurbita[6]urea, was added within 30 min. The reaction was continued at 85°C for 24 h. After cooling to room temperature, an equal volume of methanol was added and the mixture was concentrated under reduced pressure to about 50 mL. 200 mL of methanol was added again to precipitate the precipitate. The precipitate was filtered and washed three times with methanol. The crude product was dissolved in a small amount of water and desalted by washing with water through a gel chromatography column. The first elution peak was collected, concentrated, and freeze-dried to obtain the all-hydroxyl product. Anhydrous N,N-dimethylformamide was mixed with anhydrous N,N-dimethylformamide at a mass ratio of 1.5:10 and stirred until completely dissolved. Anhydrous triethylamine, at a mass ratio of 2:1 (the total hydroxyl product), was added as an acid-binding agent. The mixture was cooled to 0°C in an ice bath under nitrogen protection. Methanesulfonyl chloride, at a mass ratio of 1.5:1 (the total hydroxyl product), was dissolved in anhydrous dichloromethane and slowly added dropwise over 1 hour. The mixture was stirred at 0°C for 2 hours, then the temperature was raised to 25°C and the reaction continued for 24 hours. The resulting triethylamine hydrochloride precipitate was filtered off. The filtrate was concentrated under reduced pressure to 1 / 3 of its original volume and slowly poured into 1 L of ice-cold diethyl ether to precipitate the precipitate. After filtration, the precipitate was washed three times with anhydrous diethyl ether. The product was dried at ℃ for 12 h to obtain the full methanesulfonate product. The full methanesulfonate product was mixed with anhydrous dimethyl sulfoxide at a mass ratio of 1:15 and stirred to dissolve. Sodium cyanide at 0.3 times the mass of the full methanesulfonate product was added. The mixture was reacted at 70℃ in the dark under nitrogen protection with stirring at 300 rpm for 48 h. After cooling to room temperature, the insoluble matter was filtered off. The filtrate was slowly poured into 1 L of ice-cold ether to precipitate the product. After filtration, the precipitate was dissolved in 50 mL of deionized water and dialyzed against deionized water for 48 h, changing the water every 6 h to remove salts. The product was then freeze-dried to obtain the full cyano product. Finally, the full cyano product... The substance was mixed with 6 mol / L hydrochloric acid at a mass ratio of 1:20 and stirred to disperse. The reaction was carried out at 100℃ for 24 h to complete the cyano hydrolysis. After cooling to room temperature, the precipitate was centrifuged at 5000 rpm for 10 min. The precipitate was washed three times with deionized water. The precipitate was dissolved in a small amount of 0.1 mol / L sodium hydroxide solution to dissolve the carboxyl group. The precipitate was washed with water and desalted by Sephadex G-25 gel chromatography column and the first elution peak was collected. The pH of the eluent was adjusted to 2 with 0.1 mol / L hydrochloric acid to ionize the carboxyl group and precipitate. After centrifugation and collection, the precipitate was washed with water until neutral and then freeze-dried to obtain the all-carboxylated cucurbita[6]urea. (3) Disperse halloysite nanotubes loaded with essential oil in an acetate-sodium acetate buffer solution at pH=5 with a solid content of 2wt%. Disperse the nanotubes at 20kHz for 2h to fully deagglomerate and expose the ends to obtain a suspension. Dissolve all-carboxylated cucurbita[6]urea in an equal mass of an acetate-sodium acetate buffer solution at pH=5. Control the mass ratio of all-carboxylated cucurbita[6]urea to halloysite nanotubes loaded with essential oil to be 1:10. Slowly drip the all-carboxylated cucurbita[6]urea solution into the suspension. Stir the reaction at 25℃ for 12h to achieve selective end-capping. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added sequentially to the reaction solution. The amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.8 times the mass of the all-carboxylated cucurbit[6]urea, and the amount of N-hydroxysuccinimide was 0.5 times the mass of the all-carboxylated cucurbit[6]urea. The reaction was stirred at 300 rpm for 6 h at 25 °C to form a covalent ester bond between the carboxyl group of the all-carboxylated cucurbit[6]urea and the Al-OH of the halloysite nanotube port, thus achieving permanent covalent end-capping. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min and washed three times with deionized water to obtain the intermediate product. The intermediate product was dispersed in a mixed solvent of toluene / water at a volume ratio of 95:5, with a solid content of 2 wt%. KH-560 was added, and the mass ratio of KH-560 to the intermediate product was controlled at 0.3:1. The reaction was stirred at 70 °C for 6 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min, washed twice with anhydrous toluene and twice with anhydrous ethanol, and dried under vacuum at 60℃ for 6 h to obtain the self-made modified halloysite. (4) Mix cashew phenol, dimethylolpropionic acid and p-toluenesulfonic acid catalyst in a mass ratio of 1:1.25:0.01, stir under nitrogen protection at 140°C, and depressurize to -0.08MPa to remove water. When the acid value dropped to 60% of the initial value, 0.35 times the mass of cashew phenol in trimethylolpropane was added, and the reaction continued for 2 hours. The product was dissolved in tetrahydrofuran, with an amount 5 times the mass of the crude product. The product was precipitated twice in n-hexane, and the volume ratio of the solution to n-hexane was 1:5. The cashew phenol derivative was obtained by vacuum drying at 60°C. The cashew phenol derivative, 1-carboxyethyl-3-methylimidazolium tetrafluoroborate, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were added to a reaction flask in a mass ratio of 1:0.4:0.4:0.02. Anhydrous N,N-dimethylformamide was added to make the total solid content 20 wt%. The reaction was carried out under nitrogen protection at 25°C with stirring for 48 hours. The precipitate was filtered off, and the filtrate was concentrated under reduced pressure at 50°C to one-quarter of the original volume. The concentrate was slowly added dropwise to anhydrous diethyl ether with vigorous stirring at 2000 rpm, at a volume ratio of 1:5. A precipitate formed, and after standing, the supernatant was discarded. This ether precipitation process was repeated three times. The final precipitate was mixed with deionized water at a mass ratio of 1:5 and placed in a dialysis bag with a molecular weight cutoff of 1000 Da. Dialysis was performed in deionized water for 48 hours, with the dialysis fluid replaced every 6 hours. The mixture was then freeze-dried at -50°C for 48 hours to obtain the self-made ionic liquid. (5) Mix 100 parts by weight of homopolymer polypropylene resin with a melt flow rate of 15 g / 10 min, 5 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of calcium stearate at 500 rpm for 3 min; reduce the speed to 200 rpm, add 10 parts by weight of self-made ionic liquid, and continue mixing for 2 min; then add 5.5 parts by weight of self-made modified halloysite nanotubes and mix for 3 min to obtain a premix. Feed the premix into a co-rotating twin-screw extruder, and set the temperatures of each section from the feeding section to the die head to 160℃, 170℃, 180℃, 190℃, 195℃, 195℃, and 190℃ respectively, with a screw speed of 200 rpm and a feed rate of 3 kg / h. Apply a vacuum of -0.08 MPa to the penultimate section to remove volatiles. After being cooled in a water bath and air-dried, the extrudate was cut into 4mm pellets by a rotary pelletizer and then molded into standard test specimens using an injection molding machine. The injection molding machine barrel temperature was set to 180-190-200-195℃, the mold temperature to 50℃, the injection pressure to 70MPa, the holding time to 13s, and the cooling time to 25s. The injection-molded specimens were annealed in an 80℃ oven for 2 hours and then slowly cooled to room temperature to further complete the dynamic covalent crosslinking reaction and eliminate internal stress, thus obtaining an antibacterial and antistatic modified polypropylene material. Example 4

[0023] (1) Halloysite nanotubes with an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m² / g were dispersed in deionized water at a solid-liquid mass ratio of 1.8:20. The mixture was sonicated at 20 kHz for 30 min, allowed to stand for 24 h, and then the upper suspension was centrifuged at 3000 rpm for 15 min. The precipitate was collected, dried at 80 °C under vacuum of -0.09 MPa for 12 h, ground through a 200-mesh sieve, and 3 mol / L hydrochloric acid was added at a solid-liquid mass ratio of 1:20. The mixture was stirred at 60 °C for 4 h, washed with deionized water until neutral, and dried under vacuum at 80 °C for 12 h to obtain activated halloysite nanotubes. Eugenol and thymol were mixed at a mass ratio of 1:1 to obtain a composite antibacterial essential oil. The activated halloysite nanotubes were placed in a double-necked flask, and the vacuum was drawn to -0.095 MPa and maintained for 30 min. The composite essential oil was slowly injected under vacuum, and the mass ratio of the essential oil to the activated halloysite nanotubes was controlled to be 1:2.5. Return to normal pressure, stir at 25℃ and 200 rpm for 12 h. Quickly rinse the surface once with anhydrous ethanol, and dry at 30℃ for 2 h to obtain halloysite nanotubes loaded with essential oil; (2) Cucurbita[6]urea and deionized water were mixed at a mass ratio of 1:200, heated to 85°C and stirred vigorously to suspend cucurbita[6]urea evenly. Potassium persulfate of 6.5 times the mass of cucurbita[6]urea was added within 30 min, and the reaction was continued at 85°C for 24 h. After cooling to room temperature, an equal volume of methanol was added, and the mixture was concentrated under reduced pressure to about 50 mL. 200 mL of methanol was added again to precipitate the precipitate. The precipitate was filtered and washed three times with methanol. The crude product was dissolved in a small amount of water, washed with water to remove desalting via gel chromatography, and the first elution peak was collected, concentrated, and freeze-dried to obtain the all-hydroxyl product. The product was mixed with anhydrous N,N-dimethylformamide at a mass ratio of 1.8:10 and stirred until completely dissolved. Anhydrous triethylamine, twice the mass of the hydroxyl product, was added as an acid-binding agent. The mixture was cooled to 0°C in an ice bath under nitrogen protection. Methanesulfonyl chloride, 1.5 times the mass of the hydroxyl product, was dissolved in anhydrous dichloromethane at a solid-liquid ratio of 1:4 and slowly added dropwise to the reaction solution over 1 hour. The mixture was stirred at 0°C for 2 hours, then the temperature was raised to 25°C and the reaction continued for 24 hours. The resulting triethylamine hydrochloride precipitate was filtered off. The filtrate was concentrated under reduced pressure to 1 / 3 of its original volume and slowly poured into 1 L of ice-cold diethyl ether to precipitate the precipitate. After filtration, the precipitate was washed three times with anhydrous diethyl ether. The product was dried at 0℃ for 12 h to obtain the full methanesulfonate product. The full methanesulfonate product was mixed with anhydrous dimethyl sulfoxide at a mass ratio of 1:15 and stirred until dissolved. Sodium cyanide at 0.3 times the mass of the full methanesulfonate product was added. The mixture was reacted at 70℃ in the dark under nitrogen protection with stirring at 300 rpm for 48 h. After cooling to room temperature, the insoluble matter was filtered off. The filtrate was slowly poured into 1 L of ice-cold diethyl ether to precipitate the product. After filtration, the precipitate was dissolved in 50 mL of deionized water and dialyzed against deionized water for 48 h, changing the water every 6 h to remove salts. The product was then freeze-dried to obtain the full cyano product. Finally, the full cyano product was... The product was mixed with 6 mol / L hydrochloric acid at a mass ratio of 1:20 and stirred to disperse. The reaction was carried out at 100℃ for 24 h to complete the cyano hydrolysis. After cooling to room temperature, the product was centrifuged at 5000 rpm for 10 min. The precipitate was washed three times with deionized water. The precipitate was dissolved in a small amount of 0.1 mol / L sodium hydroxide solution to dissolve the carboxyl group. The product was washed with water and desalted by Sephadex G-25 gel chromatography column and the first elution peak was collected. The pH of the eluent was adjusted to 2 with 0.1 mol / L hydrochloric acid to ionize the carboxyl group and precipitate. After centrifugation and collection, the product was washed with water until neutral and then freeze-dried to obtain the all-carboxylated cucurbita[6]urea. (3) Disperse halloysite nanotubes loaded with essential oil in an acetate-sodium acetate buffer solution at pH=5 with a solid content of 2.5wt%. Disperse the nanotubes at 20kHz for 2h to fully deagglomerate and expose the ends to obtain a suspension. Dissolve all-carboxylated cucurbita[6]urea in an equal mass of an acetate-sodium acetate buffer solution at pH=5. Control the mass ratio of all-carboxylated cucurbita[6]urea to halloysite nanotubes loaded with essential oil to be 1.3:10. Slowly drip the all-carboxylated cucurbita[6]urea solution into the suspension. Stir the reaction at 25℃ for 12h to achieve selective end-capping. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added sequentially to the reaction solution. The amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.8 times the mass of the all-carboxylated cucurbit[6]urea, and the amount of N-hydroxysuccinimide was 0.5 times the mass of the all-carboxylated cucurbit[6]urea. The reaction was stirred at 300 rpm for 6 h at 25 °C to form a covalent ester bond between the carboxyl group of the all-carboxylated cucurbit[6]urea and the Al-OH of the halloysite nanotube port, thus achieving permanent covalent end-capping. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min and washed three times with deionized water to obtain the intermediate product. The intermediate product was dispersed in a mixed solvent of toluene / water at a volume ratio of 95:5, with a solid content of 2 wt%. KH-560 was added, and the mass ratio of KH-560 to the intermediate product was controlled at 0.3:1. The reaction was stirred at 70 °C for 6 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min, washed twice with anhydrous toluene and twice with anhydrous ethanol, and dried under vacuum at 60℃ for 6 h to obtain the self-made modified halloysite. (4) Mix cashew phenol, dimethylolpropionic acid and p-toluenesulfonic acid catalyst in a mass ratio of 1:1.4:0.01, stir at 140°C under nitrogen protection, and reduce pressure to -0.08MPa to remove water. When the acid value dropped to 60% of the initial value, 0.35 times the mass of cashew phenol in trimethylolpropane was added, and the reaction continued for 2 hours. The product was dissolved in tetrahydrofuran, with an amount 5 times the mass of the crude product. The product was precipitated twice in n-hexane, and the volume ratio of the solution to n-hexane was 1:5. The cashew phenol derivative was obtained by vacuum drying at 60°C. The cashew phenol derivative, 1-carboxyethyl-3-methylimidazolium tetrafluoroborate, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were added to a reaction flask in a mass ratio of 1:0.4:0.4:0.02. Anhydrous N,N-dimethylformamide was added to make the total solid content 20 wt%. The reaction was carried out under nitrogen protection at 25°C with stirring for 48 hours. The precipitate was filtered off, and the filtrate was concentrated under reduced pressure at 50°C to one-quarter of the original volume. The concentrate was slowly added dropwise to anhydrous diethyl ether with vigorous stirring at 2000 rpm, at a volume ratio of 1:5. A precipitate formed, and after standing, the supernatant was discarded. This ether precipitation process was repeated three times. The final precipitate was mixed with deionized water at a mass ratio of 1:5 and placed in a dialysis bag with a molecular weight cutoff of 1000 Da. Dialysis was performed in deionized water for 48 hours, with the dialysis fluid replaced every 6 hours. The mixture was then freeze-dried at -50°C for 48 hours to obtain the self-made ionic liquid. (5) Mix 105 parts by weight of homopolymer polypropylene resin with a melt flow rate of 15 g / 10 min, 5.5 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of calcium stearate at 500 rpm for 3 min; reduce the speed to 200 rpm, add 13 parts by weight of self-made ionic liquid, and continue mixing for 2 min; then add 7 parts by weight of self-made modified halloysite nanotubes and mix for 3 min to obtain a premix. Feed the premix into a co-rotating twin-screw extruder, and set the temperatures of each section from the feeding section to the die head to 160℃, 170℃, 180℃, 190℃, 195℃, 195℃, and 190℃ respectively, with a screw speed of 200 rpm and a feed rate of 3 kg / h. Apply a vacuum of -0.08 MPa to the penultimate section to remove volatiles. After being cooled in a water bath and air-dried, the extrudate was cut into 4.5mm pellets by a rotary pelletizer and then molded into standard test specimens using an injection molding machine. The injection molding machine barrel temperature was set to 180-190-200-195℃, the mold temperature to 50℃, the injection pressure to 70MPa, the holding time to 13s, and the cooling time to 25s. The injection-molded specimens were annealed in an 80℃ oven for 2 hours and then slowly cooled to room temperature to further complete the dynamic covalent cross-linking reaction and eliminate internal stress, thus obtaining an antibacterial and antistatic modified polypropylene material. Example 5

[0024] (1) Halloysite nanotubes with an outer diameter of 50 nm, an inner diameter of 20 nm, a length of 1 μm, and a specific surface area ≥ 50 m² / g were dispersed in deionized water at a solid-liquid mass ratio of 2:20. The mixture was sonicated at 20 kHz for 30 min, allowed to stand for 24 h, and then the upper suspension was centrifuged at 3000 rpm for 15 min. The precipitate was collected, dried at 80 °C under vacuum of -0.09 MPa for 12 h, ground through a 200-mesh sieve, and 3 mol / L hydrochloric acid was added at a solid-liquid mass ratio of 1:20. The mixture was stirred at 60 °C for 4 h, washed with deionized water until neutral, and dried under vacuum at 80 °C for 12 h to obtain activated halloysite nanotubes. Eugenol and thymol were mixed at a mass ratio of 1:1 to obtain a composite antibacterial essential oil. The activated halloysite nanotubes were placed in a double-necked flask, and the vacuum was drawn to -0.095 MPa and maintained for 30 min. The composite essential oil was slowly injected under vacuum, and the mass ratio of the essential oil to the activated halloysite nanotubes was controlled at 1:3. Return to normal pressure, stir at 25℃ and 200 rpm for 12 h. Quickly rinse the surface once with anhydrous ethanol, and dry at 30℃ for 2 h to obtain halloysite nanotubes loaded with essential oil; (2) Cucurbita[6]urea and deionized water were mixed at a mass ratio of 1:200, heated to 85°C and stirred vigorously to suspend cucurbita[6]urea evenly. Then, potassium persulfate was added at a mass ratio of 7 times that of cucurbita[6]urea within 30 min, and the reaction was continued at 85°C for 24 h. After cooling to room temperature, an equal volume of methanol was added, and the mixture was concentrated under reduced pressure to about 50 mL. Then, 200 mL of methanol was added again to precipitate the precipitate. The precipitate was filtered and washed three times with methanol. The crude product was dissolved in a small amount of water, washed with water to remove desalting via gel chromatography, and the first elution peak was collected, concentrated, and freeze-dried to obtain the all-hydroxyl product. Anhydrous N,N-dimethylformamide was mixed with anhydrous N,N-dimethylformamide at a mass ratio of 2:10 and stirred until completely dissolved. Anhydrous triethylamine, at a mass ratio of 2:10, was added as an acid-binding agent. The mixture was cooled to 0°C in an ice bath under nitrogen protection. Methanesulfonyl chloride, at a mass ratio of 1.5:10, was dissolved in anhydrous dichloromethane and slowly added dropwise over 1 hour. The mixture was stirred at 0°C for 2 hours, then the temperature was raised to 25°C and the reaction continued for 24 hours. The resulting triethylamine hydrochloride precipitate was filtered off. The filtrate was concentrated under reduced pressure to 1 / 3 of its original volume and slowly poured into 1 L of ice-cold diethyl ether to precipitate the precipitate. After filtration, the precipitate was washed three times with anhydrous diethyl ether and then cooled at 40°C. The product was dried for 12 hours to obtain the full methanesulfonate product. The full methanesulfonate product was then mixed with anhydrous dimethyl sulfoxide at a mass ratio of 1:15 and stirred until dissolved. Sodium cyanide at 0.3 times the mass of the full methanesulfonate product was added. The mixture was reacted at 70°C under nitrogen protection, stirred at 300 rpm for 48 hours. After cooling to room temperature, the insoluble matter was filtered off. The filtrate was slowly poured into 1 L of ice-cold ether to precipitate the product. The precipitate was dissolved in 50 mL of deionized water and dialyzed against deionized water for 48 hours, changing the water every 6 hours to remove salts. The product was then freeze-dried to obtain the full cyano product. Finally, the full cyano product... The substance was mixed with 6 mol / L hydrochloric acid at a mass ratio of 1:20 and stirred to disperse. The reaction was carried out at 100℃ for 24 h to complete the cyano hydrolysis. After cooling to room temperature, the precipitate was centrifuged at 5000 rpm for 10 min. The precipitate was washed three times with deionized water. The precipitate was dissolved in a small amount of 0.1 mol / L sodium hydroxide solution to dissolve the carboxyl group. The precipitate was washed with water and desalted by Sephadex G-25 gel chromatography column and the first elution peak was collected. The pH of the eluent was adjusted to 2 with 0.1 mol / L hydrochloric acid to ionize the carboxyl group and precipitate. After centrifugation and collection, the precipitate was washed with water until neutral and then freeze-dried to obtain the all-carboxylated cucurbita[6]urea. (3) Disperse halloysite nanotubes loaded with essential oil in an acetate-sodium acetate buffer solution at pH=5 with a solid content of 3wt%. Disperse the nanotubes by ultrasonication at 20kHz for 2h to fully deagglomerate them and expose the ends to obtain a suspension. Dissolve all-carboxylated cucurbita[6]urea in an equal mass of an acetate-sodium acetate buffer solution at pH=5. Control the mass ratio of all-carboxylated cucurbita[6]urea to halloysite nanotubes loaded with essential oil to be 1.5:10. Slowly drip the all-carboxylated cucurbita[6]urea solution into the suspension. Stir the reaction at 25℃ for 12h to achieve selective end-capping. Subsequently, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide were added sequentially to the reaction solution. The amount of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.8 times the mass of the all-carboxylated cucurbit[6]urea, and the amount of N-hydroxysuccinimide was 0.5 times the mass of the all-carboxylated cucurbit[6]urea. The reaction was stirred at 300 rpm for 6 h at 25 °C to form a covalent ester bond between the carboxyl group of the all-carboxylated cucurbit[6]urea and the Al-OH of the halloysite nanotube port, thus achieving permanent covalent end-capping. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min and washed three times with deionized water to obtain the intermediate product. The intermediate product was dispersed in a mixed solvent of toluene / water at a volume ratio of 95:5, with a solid content of 2 wt%. KH-560 was added, and the mass ratio of KH-560 to the intermediate product was controlled at 0.3:1. The reaction was stirred at 70 °C for 6 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 5000 rpm for 10 min, washed twice with anhydrous toluene and twice with anhydrous ethanol, and dried under vacuum at 60℃ for 6 h to obtain the self-made modified halloysite. (4) Mix cashew phenol, dimethylolpropionic acid and p-toluenesulfonic acid catalyst in a mass ratio of 1:1.5:0.01, stir under nitrogen protection at 140°C, and reduce pressure to -0.08MPa to remove water. When the acid value dropped to 60% of the initial value, 0.35 times the mass of cashew phenol in trimethylolpropane was added, and the reaction continued for 2 hours. The product was dissolved in tetrahydrofuran, with an amount 5 times the mass of the crude product. The product was precipitated twice in n-hexane, and the volume ratio of the solution to n-hexane was 1:5. The cashew phenol derivative was obtained by vacuum drying at 60°C. The cashew phenol derivative, 1-carboxyethyl-3-methylimidazolium tetrafluoroborate, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine were added to a reaction flask in a mass ratio of 1:0.4:0.4:0.02. Anhydrous N,N-dimethylformamide was added to make the total solid content 20 wt%. The reaction was carried out under nitrogen protection at 25°C with stirring for 48 hours. The precipitate was filtered off, and the filtrate was concentrated under reduced pressure at 50°C to one-quarter of the original volume. The concentrate was slowly added dropwise to anhydrous diethyl ether with vigorous stirring at 2000 rpm, at a volume ratio of 1:5. A precipitate formed, and after standing, the supernatant was discarded. This ether precipitation process was repeated three times. The final precipitate was mixed with deionized water at a mass ratio of 1:5 and placed in a dialysis bag with a molecular weight cutoff of 1000 Da. Dialysis was performed in deionized water for 48 hours, with the dialysis fluid replaced every 6 hours. The mixture was then freeze-dried at -50°C for 48 hours to obtain the self-made ionic liquid. (5) Mix 110 parts by weight of homopolymer polypropylene resin with a melt flow rate of 15 g / 10 min, 6 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant 1010, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of calcium stearate at 500 rpm for 3 min; reduce the speed to 200 rpm, add 15 parts by weight of self-made ionic liquid, and continue mixing for 2 min; then add 8 parts by weight of self-made modified halloysite nanotubes and mix for 3 min to obtain a premix. Feed the premix into a co-rotating twin-screw extruder, and set the temperatures of each section from the feeding section to the die head to 160℃, 170℃, 180℃, 190℃, 195℃, 195℃, and 190℃ respectively, with a screw speed of 200 rpm and a feed rate of 3 kg / h. Apply a vacuum of -0.08 MPa to the penultimate section to remove volatiles. After being cooled in a water bath and air-dried, the extrudate was cut into 5mm pellets by a rotary pelletizer and then molded into standard test specimens using an injection molding machine. The injection molding machine barrel temperature was set to 180-190-200-195℃, the mold temperature to 50℃, the injection pressure to 70MPa, the holding time to 13s, and the cooling time to 25s. The injection-molded specimens were annealed in an 80℃ oven for 2 hours and then slowly cooled to room temperature to further complete the dynamic covalent cross-linking reaction and eliminate internal stress, thus obtaining an antibacterial and antistatic modified polypropylene material.

[0025] Comparative Example 1 The difference between Comparative Example 1 and Example 3 is that no homemade ionic liquid is added; the other steps are the same as in Example 3.

[0026] Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that the self-made modified halloysite nanotubes are not added, while the other steps are the same as in Example 3.

[0027] Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that the self-made modified halloysite nanotubes were replaced with an equal amount of untreated natural halloysite nanotubes, while the other steps were the same as in Example 3.

[0028] Comparative Example 4 The difference between Comparative Example 4 and Example 3 is that the self-made modified halloysite nanotubes were replaced with an equal amount of uncapped halloysite nanotubes loaded with eugenol / thymol essential oil. The remaining steps are the same as in Example 3.

[0029] Comparative Example 5 The difference between Comparative Example 5 and Example 3 is that PP-g-GMA is not added; the other steps are the same as in Example 3.

[0030] Comparative Example 6 The difference between Comparative Example 6 and Example 3 is that the self-made ionic liquid was replaced with a physical mixture of cashew phenol and 1-carboxyethyl-3-methylimidazolium tetrafluoroborate in equal molar amounts of hydroxyl groups, while the other steps were the same as in Example 3.

[0031] Example of effect Table 1 below shows the performance analysis results of the modified PP materials of Examples 1 to 5 and Comparative Examples 1 to 6 of the present invention.

[0032]

[0033] Comparison of the experimental data on antibacterial rates of the examples and comparative examples reveals that the present invention first loads halloysite nanotubes with thymol / eugenol composite essential oil via vacuum suction, and then uses carboxylated cucurbita[6]urea to perform supramolecular encapsulation and sealing at the tube ends, and then modifies the surface with KH-560 to graft epoxy groups to obtain self-made modified halloysite; secondly, using biomass cashew phenol as the core, it obtains self-made ionic liquid through polycondensation with dimethylolpropionic acid and partial esterification and end-capping with 1-carboxyethyl-3-methylimidazolium tetrafluoroborate; during the melt extrusion process, the residual hydroxyl and carboxyl groups of the self-made ionic liquid simultaneously undergo ring-opening with the modified halloysite and PP-g-GMA to obtain antibacterial and antistatic modified PP material, and the slow-release long-term effect of cucurbita-terminated plant essential oil. The rapid bactericidal effect of the contact between the effective bactericidal agent and the imidazole salt of the ionic liquid forms a slow-release, contact antibacterial mechanism, endowing the material with excellent antibacterial properties. A comparison of the surface resistivity experimental data from the examples and comparative examples reveals that the imidazole cation-tetrafluoroborate ion pair of the self-made ionic liquid in this invention constructs an efficient ion conduction pathway, while the trace amounts of moisture bound by halloysite nanochannels assist in ion hopping transport. The synergistic effect of both allows the material to maintain excellent antistatic properties even under low humidity. A comparison of the tensile strength retention data from the examples and comparative examples reveals that the free radical scavenging and antioxidant capacity imparted by the cashew phenolic aldehyde structure in this invention, combined with the labyrinth barrier effect of the halloysite sheets, significantly improves the long-term heat and oxygen aging stability of the material.

[0034] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing an antibacterial and antistatic modified PP material, characterized in that, Includes the following steps: (1) Halloysite nanotubes were dispersed in water, sonicated, centrifuged and activated with hydrochloric acid to obtain activated halloysite; composite antibacterial essential oil was vacuum loaded onto activated halloysite, washed with ethanol and dried to obtain halloysite nanotubes loaded with essential oil; cucurbit[6]urea and deionized water were mixed at a mass ratio of 1:200, and potassium persulfate of 5 to 7 times the mass of cucurbit[6]urea was added under stirring at 85°C and reacted for 24 h. The product was obtained by methanol precipitation and gel chromatography desalting. Then, after sequential esterification with methanesulfonyl chloride, cyanation with sodium cyanide, and hydrolysis with hydrochloric acid, carboxylation was performed to obtain fully carboxylated cucurbita[6]urea; halloysite loaded with essential oil was dispersed in a buffer solution, and 0.05~0.15 times the mass of halloysite loaded with essential oil was added to fully carboxylated cucurbita[6]urea. After covalent end-capping catalyzed by an activating agent and modification with silane, the self-made modified halloysite was obtained. (2) Cashew phenol, dimethylolpropionic acid and catalyst were mixed at a mass ratio of 1:1~1.5:0.01 and reacted under reduced pressure under nitrogen protection at 140°C. Trimethylolpropane with a mass of 0.35 times that of cashew phenol was added and the reaction was continued for 2 hours. After organic dissolution, hexane precipitation and drying, cashew phenol derivative was obtained. It was mixed with ionic liquid precursor and reacted at 25°C for 48 hours. After precipitation and dialyzing for 48 hours, the self-made ionic liquid was obtained by freeze drying. (3) 90-110 parts by weight of homopolymer polypropylene resin, 4-6 parts by weight of PP-g-GMA, 0.2 parts by weight of antioxidant A, 0.3 parts by weight of antioxidant B, 0.5 parts by weight of calcium stearate, 5-15 parts by weight of self-made ionic liquid, and 3-8 parts by weight of self-made modified halloysite nanotubes are mixed and then extruded, injection molded and annealed to obtain antibacterial and antistatic modified PP material.

2. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The halloysite nanotubes mentioned in step (1) have the following characteristics: outer diameter 50 nm, inner diameter 20 nm, length 1 μm, and specific surface area ≥ 50 m². 2 / g.

3. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The compound antibacterial essential oil mentioned in step (1) is prepared by mixing eugenol and thymol in a mass ratio of 1:

1.

4. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The activating agent in step (1) is a mixed solution of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in an amount 0.8 times the mass of all-carboxylated cucurbit[6]urea and N-hydroxysuccinimide in an amount 0.5 times the mass of all-carboxylated cucurbit[6]urea.

5. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The silane mentioned in step (1) is KH-560.

6. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The catalyst in step (2) is p-toluenesulfonic acid.

7. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The ionic liquid precursor in step (2) is 1-carboxyethyl-3-methylimidazolium tetrafluoroborate.

8. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The homopolymer polypropylene resin used in step (3) has a melt flow rate of 15 g / 10 min.

9. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The antioxidant A mentioned in step (3) is antioxidant 1010.

10. The antibacterial and antistatic modified PP material according to claim 1, characterized in that, The antioxidant B mentioned in step (3) is antioxidant 168.

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