Antistatic polypropylene master batch, preparation method and application in polypropylene fiber

Abstract

The invention relates to the technical field of high-molecular compound compositions, and discloses an antistatic polypropylene master batch, a preparation method and application in polypropylene fibers. The preparation method of the antistatic polypropylene master batch comprises the following steps: polymerizing a boron-containing compound and a quaternary ammonium salt compound to obtain a biopolymer; the modified Mxene nanosheet and the modified superfine Ce-MOF nanorod are combined, and a hybrid inorganic filler is obtained; reacting the hybrid inorganic filler with the bipolymer to obtain a modified hybrid inorganic filler; the pretreated polypropylene and the intermediate product are subjected to a reaction and extrusion, and surface modified polypropylene is obtained; modifying the surface modified polypropylene with a modifier, mixing with the modified hybrid inorganic filler, extruding, and granulating to obtain the antistatic polypropylene master batch. The antistatic polypropylene master batch provided by the invention not only has excellent antistatic performance, but also has the advantages of moisture absorption, flame retardance and antibacterial property, and can be used in polypropylene fibers.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of high-molecular compound compositions, in particular to an antistatic polypropylene master batch, a preparation method and application in polypropylene fiber. BACKGROUND

[0002] Polypropylene (PP) is a semi-crystalline polymer, which has excellent mechanical properties, heat resistance, chemical resistance and easy formability. However, the polypropylene molecular structure lacks hydrophilic groups, and the surface energy is small, so the surface wettability and hydrophilicity of polypropylene are poor, thereby limiting its application in clothing, sanitary materials and industrial fields. With the development of technology, higher requirements are put forward for polypropylene fiber (i.e. polypropylene fiber) in traditional application fields of polypropylene fiber, such as the demand for comfort of non-woven fabric and clothing products, the demand for good skin and moisture absorption of polypropylene fiber, the demand for safety in the process of fiber post-processing and use, and the demand for good antistatic performance of the fiber. Adding fillers to the polypropylene master batch to improve the moisture absorption and antistatic performance of the polypropylene master batch is one of the common methods for improving the moisture absorption and antistatic performance of polypropylene fiber.

[0003] For example, Chinese patent CN 112759848B discloses an antibacterial and antistatic polypropylene composite material and a preparation method thereof. The antibacterial and antistatic polypropylene composite material disclosed in the application comprises polypropylene resin, toughening agent and talc powder, the total mass fraction of the polypropylene resin, the toughening agent and the talc powder is 100 parts, and further comprises 2-10 parts of antibacterial and antistatic master batch, 0.2-0.6 parts of antioxidant, 0.05-0.3 parts of lubricant and 0.2-0.5 parts of weather-resistant agent. The antibacterial and antistatic master batch is prepared from antibacterial and antistatic pre-compound and polypropylene as raw materials. The antibacterial and antistatic pre-compound is prepared from nano-silver, graphene oxide and coupling agent as raw materials. However, the graphene oxide component in the antibacterial and antistatic pre-compound has the problems of easy agglomeration and poor dispersibility in the matrix.

[0004] In addition, with the development of science and technology, the improvement of living standards and the enhancement of health and environmental protection consciousness, higher requirements are put forward for polypropylene fiber in the fields of clothing, household and industry, such as polypropylene materials with antibacterial and flame-retardant functions, which are important research objects. Therefore, it is also crucial to improve the antibacterial and flame-retardant properties of polypropylene materials. SUMMARY

[0005] In order to solve the above technical problems, the application provides a preparation method of a moisture-absorbing and sweat-releasing woven tape, which comprises the following steps: Step one, polymerization of a boron-containing compound and a quaternary ammonium salt compound to obtain a binary copolymer; Step two, combine the modified Mxene nanosheet with the modified ultra-fine Ce-MOF nanorod to obtain a hybrid inorganic filler; the hybrid inorganic filler is reacted with a binary copolymer to obtain a modified hybrid inorganic filler; Step three, maleic anhydride is reacted with p-phenylenediamine to obtain an intermediate product; the pretreated polypropylene, the intermediate product, and 2,5-bis(tert-butyl peroxy)-2,5-dimethylhexane are mixed and extruded to obtain a surface-modified polypropylene; the surface-modified polypropylene is modified by a modifier to obtain a grafted modified polypropylene; the grafted modified polypropylene is mixed with the modified hybrid inorganic filler, extruded and granulated to obtain an antistatic polypropylene masterbatch.

[0006] Preferably, in the step one, the preparation method of the binary copolymer specifically comprises: weighing N,N-dimethyl ethanolamine, acetone and allyl chloride according to the mass ratio of (6.8-13.4):(150-200):(7.7-15.3), reacting at 38-42℃ for 22-26h, purifying to obtain a quaternary ammonium salt compound; mixing boric acid and 4-buten-1-ol in a mass ratio of (1.5-3.1):(6.5-12.9), reacting at 128-132℃ to obtain a boron-containing compound; adding the boron-containing compound into deionized water, stirring, then adding the quaternary ammonium salt compound, purging with nitrogen, then adding 5wt% hydrogen peroxide solution and ferric chloride, reacting at 65-75℃ for 2-4h, purifying to obtain the binary copolymer; wherein the mass ratio of the boron-containing compound, deionized water, quaternary ammonium salt compound, 5wt% hydrogen peroxide solution and ferric chloride is (8-16):(200-300):(4.1-8.2):(0.5-1.1):(0.04-0.06); in the above process, N,N-dimethyl ethanolamine and allyl chloride are combined by quaternary ammonium reaction to obtain a quaternary ammonium salt compound containing carbon-carbon double bond and hydroxyl group; boric acid and 4-buten-1-ol are dehydrated and condensed to obtain a boron-containing compound containing carbon-carbon double bond; the boron-containing compound is polymerized under the catalytic action to form a binary copolymer, which contains hydrophilic, antibacterial quaternary ammonium salt structure, hydrophilic hydroxyl group, carbon-carbon double bond and flame-retardant boron element.

[0007] Preferably, in step two, the preparation method of the modified hybrid inorganic filler specifically includes: weighing aminated Mxene nanosheets, dimethyl sulfoxide, and 4-mercaptobenzaldehyde in a mass ratio of (3-5):(120-150):(0.2-0.5), reacting at 80-100℃ for 8-10 h, and purifying to obtain modified Mxene nanosheets; mixing the modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol in a mass ratio of 1:(0.2-0.4):100, sonicating, reacting in a nitrogen atmosphere at 60-70℃ for 8-10 h, and purifying to obtain the hybrid inorganic filler; adding the hybrid inorganic filler to ethanol, sonicating, heating to 60-70℃, and then adding a binary co-polymer... The polymer and a 0.5 wt% azobisisobutyronitrile / ethanol mixed solution were stirred and reacted for 3-5 h, then purified to obtain the modified hybrid inorganic filler. The mass ratio of the hybrid inorganic filler, ethanol, binary copolymer, and 0.5 wt% azobisisobutyronitrile / ethanol mixed solution was (3-5):(120-150):(3.6-6.4):(10-16). During this process, the amino group of the aminated Mxene nanosheets reacts with the aldehyde group of 4-mercaptobenzaldehyde to generate a Schiff base bond, introducing thiol groups onto the Mxene nanosheets to obtain modified Mxene nanosheets. Next, the Schiff base bond of the modified Mxene nanosheets undergoes a pH addition reaction with dimethyl phosphate on the modified ultrafine Ce-MOF nanorods, thus modifying the ultrafine Ce-MOF nanorods. F nanorods loaded on modified Mxene nanosheets yield hybrid inorganic fillers. Mxene nanosheets not only possess excellent electrical conductivity, hydrophilicity, and photothermal antibacterial properties, but also undergo thermal oxidation to titanium dioxide during combustion, promoting matrix carbonization and improving char layer quality. Furthermore, the layered structure of Mxene nanosheets provides a physical barrier, extending the diffusion path of pyrolysis volatiles and reducing their emissions, thus exhibiting excellent flame-retardant properties. Modified ultrafine Ce-MOF nanorods loaded on modified Mxene nanosheets can act as bridging points, forming a complex conductive network, improving conductivity, and exhibiting better antistatic properties. In addition, modified ultrafine Ce... - MOF nanorods loaded with modified Mxene nanosheets can also exert a synergistic flame-retardant effect. Furthermore, the thiol groups on the hybrid inorganic filler undergo a click reaction with the carbon-carbon double bonds of the binary copolymer, organically linking the binary copolymer onto the hybrid inorganic filler. The presence of hydrophilic / antibacterial quaternary ammonium salt structures, hydrophilic hydroxyl groups, and flame-retardant boron elements in the binary copolymer improves the hydrophilicity, antistatic properties, antibacterial properties, and flame-retardant properties of the hybrid inorganic filler. At the same time, the organic chains of the binary copolymer crosslink with polypropylene and form hydrogen bonds with the grafted modified polypropylene, improving the dispersibility of the hybrid inorganic filler and increasing the crosslinking density of the polypropylene system. While maintaining the mechanical properties of the polypropylene matrix, it improves the antibacterial properties, hygroscopic properties, antistatic properties, and flame-retardant properties.

[0008] Furthermore, the aminated Mxene nanosheets are prepared by the following steps: Step A1: Mix MAX phase Ti3AlC2 powder, lithium fluoride, and 9 mol / L hydrochloric acid aqueous solution at a mass ratio of (2-4):(2-4):(19-38), stir at 36-40℃ for 40-50 h, centrifuge, wash, add the washed precipitate to deionized water, sonicate in a nitrogen atmosphere for 50-70 min, centrifuge, freeze dry to obtain Mxene nanosheets; mix Mxene nanosheets and dimethyl sulfoxide at a mass ratio of (1-3):(50-80), sonicate for 20-40 min, stir in a nitrogen atmosphere for 45-50 h, purify to obtain hydroxylated Mxene nanosheets; Step A2: Mix silane coupling agent KH-550 and ethanol / water mixture at a mass ratio of (1-3):41, adjust pH to 4.5, and pre-hydrolyze for 2 hours to obtain silane coupling agent KH-550 hydrolysate; mix hydroxylated Mxene nanosheets and ethanol / water mixture at a mass ratio of (3-5):41, sonicate, then add the above silane coupling agent KH-550 hydrolysate, stir and react for 6-8 hours at 28-32℃ under nitrogen atmosphere, purify, and obtain aminated Mxene nanosheets; in the above process, MAX phase Ti3AlC2 powder is etched with lithium fluoride and hydrochloric acid, and then sonicated to obtain Mxene nanosheets; further, the Mxene nanosheets are treated to make their surface rich in hydroxyl groups, and then treated with silane coupling agent KH-550 to obtain aminated Mxene nanosheets.

[0009] Furthermore, the modified ultrafine Ce-MOF nanorods are prepared by the following steps: Step B1: Sodium hydroxide, trimesic acid, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are mixed in a ratio of (0.04-0.08) g : (0.07-0.14) g : (3-6) g : (60-120) mL : (2-4) mL, and vortexed for 30 s to obtain the ligand micelle phase; cerium nitrate hexahydrate, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are mixed in a ratio of (0.04-0.08) g : (0.07-0.14) g : (3-6) g : (60-120) mL : (2-4) mL, and the mixture is vortexed for 30 s to obtain the ligand micelle phase; cerium nitrate hexahydrate, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are .... A 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution was mixed at a ratio of (0.14-0.28) g: (2-4) g: (40-80) mL: (1-2) mL, sonicated, and the above ligand micelle phase was added dropwise over 1 hour. The mixture was reacted at 38-42℃ for 2.5-3.5 hours, followed by the addition of 30 wt% hydrogen peroxide aqueous solution and the reaction at 24-26℃ for 50-70 minutes. After purification, ultrafine Ce-MOF nanorods with an average diameter of 50 nm were obtained. Step B2: Ultrafine Ce-MOF nanorods, ethanol, and a 0.002 g / mL dimethyl phosphate / ethanol mixture are mixed at a mass ratio of (1-3):(80-100):(80-120). The mixture is stirred at 58-62℃ for 50-70 min, purified, and the modified ultrafine Ce-MOF nanorods are obtained. In the above process, an anion-cation micelle system is used to prepare ultrafine Ce-MOF nanorods with an average diameter of 50 nm. The micelles provide a stable crystal growth chamber and improve the growth continuity of Ce-MOF, thus resulting in smaller Ce-MOF nanorod sizes. Then, dimethyl phosphate reacts with C through its P=O moiety. Ce undergoes strong coordination in the e-MOF, thereby introducing a dimethyl phosphate structure onto the ultrafine Ce-MOF nanorods. The ultrafine MOF in this invention can effectively solve the problem of insufficient conductivity in MOF materials, resulting in Ce-MOFs with good conductivity. In addition, Ce-MOF nanorods can release cerium ions during combustion, promoting the formation of a carbon layer, and their porous structure can adsorb flammable gases. Therefore, Ce-MOF nanorods also have good flame retardant properties. Furthermore, the introduction of a dimethyl phosphate structure onto the ultrafine Ce-MOF nanorods introduces flame-retardant phosphorus, thereby enhancing the flame retardant performance of the ultrafine Ce-MOF nanorods.

[0010] Preferably, in step three, the preparation method of the surface-modified polypropylene specifically includes: adding maleic anhydride to toluene, adding a 9.2wt% p-phenylenediamine / ethyl ether mixture, reacting at 20-24℃ for 3.5-4.5h, evaporating the solvent to obtain an intermediate product; wherein the mass ratio of maleic anhydride, toluene, and 9.2wt% p-phenylenediamine / ethyl ether mixture is (2.4-4.9):65:(29.3-58.7); mixing caffeic acid and thionyl chloride at a mass ratio of (1.8-3.6):(5.2-11.8), stirring, reacting at 76-84℃ for 20-30min, distilling to obtain a modifier; and mixing polypropylene particles with 0.5wt% p-phenylenediamine / ethyl ether mixture. A mixture of 2,6-di-tert-butyl-p-cresol / acetone is mixed at a mass ratio of (10-12):(200-300), stirred for 40-60 min, and rotary evaporated to obtain pretreated polypropylene; the pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane are mixed at a mass ratio of 100:(0.3-0.5):0.2, extruded at 190-200℃ and 20-25 rpm, purified, to obtain surface-modified polypropylene; preferably, in step three, the preparation method of the grafted modified polypropylene specifically includes: adding surface-modified polypropylene to N,N-dimethylformamide, sonicating, then adding a modifier, stirring and reacting at room temperature for 12-14 h, and purifying to obtain grafted modified polypropylene; wherein, the mass ratio of surface-modified polypropylene, N,N-dimethylformamide, and modifier is (8- 10): (100-150): (9.9-14.9); In the above process, maleic anhydride reacts with the amino group at one end of p-phenylenediamine to obtain an intermediate product; while caffeic acid reacts with thionyl chloride to convert the carboxyl group in caffeic acid into acyl chloride to obtain a modifier; next, 2,6-di-tert-butyl-p-cresol is used to stabilize polypropylene to obtain pretreated polypropylene. The pretreated polypropylene and the intermediate product are combined through an addition reaction to obtain surface-modified polypropylene. Abundant amino groups are introduced on the surface of polypropylene to provide reactive groups for polypropylene. Moreover, the amino groups have good hydrophilicity and can improve the moisture absorption, air permeability and antistatic properties of polypropylene; finally, the amino groups of the surface-modified polypropylene react with the acyl chloride in the modifier to graft the caffeic acid structure onto the polypropylene branch chain, introduce the catechol structure, endow polypropylene with antibacterial properties, and further improve the moisture absorption and antistatic properties of polypropylene.

[0011] Preferably, in step three, the mass ratio of the grafted modified polypropylene to the modified hybrid inorganic filler is (5-9):(2-4.5); the extrusion process parameters are: zone 1 temperature 160-180℃, zone 2 temperature 165-185℃, zone 3 temperature 170-190℃, zone 4 temperature 175-195℃, zone 5 temperature 180-200℃, zone 6 temperature 180-200℃, zone 7 temperature 185-205℃, zone 8 temperature 190-210℃, die temperature 190-210℃, and screw speed 400-600 rpm.

[0012] The antistatic polypropylene masterbatch prepared by the aforementioned method is described.

[0013] Application of the antistatic polypropylene masterbatch in polypropylene fiber.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention obtains a hybrid inorganic filler by loading modified ultrafine Ce-MOF nanorods onto modified Mxene nanosheets. The modified ultrafine Ce-MOF nanorods can serve as bridging points for the Mxene nanosheets, forming a complex conductive network, improving conductivity, and exhibiting better antistatic properties. In addition, the ultrafine Ce-MOF nanorods themselves have flame-retardant properties, which are further improved after modification with dimethyl phosphate. Therefore, the modified ultrafine Ce-MOF nanorods and modified Mxene nanosheets can also exert a synergistic flame-retardant effect. Furthermore, the organic links of the binary copolymer are grafted onto the hybrid inorganic filler, which can improve the hydrophilicity, antistatic properties, antibacterial properties, and flame-retardant properties of the hybrid inorganic filler. At the same time, the organic chains of the binary copolymer crosslink with polypropylene and form hydrogen bonds with the grafted modified polypropylene, improving the dispersibility of the hybrid inorganic filler and increasing the crosslinking density of the polypropylene system. While maintaining the mechanical properties of the polypropylene matrix, the antibacterial properties, hygroscopic properties, antistatic properties, and flame-retardant properties are improved. 2. This invention modifies polypropylene by grafting, introducing abundant amino groups onto the surface of polypropylene to provide reactive groups and improve the moisture absorption, breathability, and antistatic properties of polypropylene; then, caffeic acid structures are grafted onto the polypropylene branches to introduce catechol structures, endowing polypropylene with antibacterial properties and further improving the moisture absorption and antistatic properties of polypropylene. 3. This invention uses an anion-cation micelle system to prepare ultrafine Ce-MOF nanorods with an average diameter of 50 nm. The smaller size of the Ce-MOF nanorods can effectively solve the problem of insufficient conductivity of MOF materials, and obtain Ce-MOF with good conductivity. 4. Applying the antistatic polypropylene masterbatch of the present invention to polypropylene fiber not only solves the problems of easy static electricity and poor moisture absorption of polypropylene fiber, but also endows polypropylene fiber with excellent flame retardant and antibacterial properties. Attached Figure Description

[0015] Figure 1 This is a comparison chart of resistivity tests of polypropylene fiber samples prepared in Examples 3-5 and Comparative Examples 1-4 of the present invention. Figure 2 This is a comparison chart of oxygen index tests of polypropylene fiber samples prepared in Examples 3-5 and Comparative Examples 1-4 of the present invention. Figure 3 This is a comparison chart of the moisture regain test results of polypropylene fiber samples prepared in Examples 3-5 and Comparative Examples 1-4 of the present invention. Figure 4 This is a comparison chart of the Staphylococcus aureus inhibition rate test of polypropylene fiber samples prepared in Examples 3-5 and Comparative Examples 1-4 of the present invention. 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. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0017] Example 1 This embodiment discloses a method for preparing aminated Mxene nanosheets, including the following steps: Step A1: Add 3g of MAX phase Ti3AlC2 powder and 3g of lithium fluoride to 28.5g of 9mol / L hydrochloric acid aqueous solution, stir at 38℃ for 45h, centrifuge, wash the resulting precipitate with deionized water until the pH of the washing solution is 6.5, add the washed precipitate to deionized water, sonicate in a nitrogen atmosphere for 60min, centrifuge, freeze-dry the upper suspension at -50℃ for 48h to obtain Mxene nanosheets; disperse 2g of Mxene nanosheets in 65g of dimethyl sulfoxide, sonicate for 30min, stir in a nitrogen atmosphere for 48h, centrifuge, wash, freeze-dry to obtain hydroxylated Mxene nanosheets; Step A2: Add 2g of silane coupling agent KH-550 to 41g of a 90% ethanol / water mixture, adjust the pH of the mixture to 4.5 with acetic acid, and pre-hydrolyze for 2h to obtain a silane coupling agent KH-550 hydrolysate; add 4g of hydroxylated Mxene nanosheets to 41g of a 90% ethanol / water mixture, sonicate for 60min, then add the above silane coupling agent KH-550 hydrolysate, and stir the reaction at 30℃ for 7h under a nitrogen atmosphere. After the reaction is completed, centrifuge, wash, and dry to obtain aminated Mxene nanosheets.

[0018] Example 2 This embodiment discloses a method for preparing modified ultrafine Ce-MOF nanorods, the specific steps of which are as follows: Step B1: Add 0.06g sodium hydroxide and 0.11g trimesic acid to 4.5g water, then add 90mL of 0.1mol / L sodium dodecyl sulfate aqueous solution and 3mL of 0.1mol / L hexadecyltrimethylammonium bromide aqueous solution, vortex for 30s to obtain ligand micelle phase; add 0.21g cerium nitrate hexahydrate to 3g water, then add 60mL of 0.1mol / L sodium dodecyl sulfate aqueous solution and 1.5mL of 0.1mol / L hexadecyltrimethylammonium bromide aqueous solution, sonicate for 4min, then add the above ligand micelle phase dropwise over 1h, react at 40℃ for 3h, then add 1.7g of 30wt% hydrogen peroxide aqueous solution, and react at 25℃ for 60min. After the reaction, centrifuge, wash the obtained solid product with deionized water and ethanol, and vacuum dry at 50℃ to obtain ultrafine Ce-MOF nanorods with an average diameter of 50nm; Step B2: Disperse 2g of ultrafine Ce-MOF nanorods in 90g of ethanol, then add 100g of a 0.002g / mL dimethyl phosphate / ethanol mixture, stir and react at 60℃ for 60min, centrifuge, wash the resulting solid product with ethanol, and vacuum dry at 80℃ to obtain modified ultrafine Ce-MOF nanorods.

[0019] Example 3 This embodiment discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 6.8g N,N-dimethylethanolamine and 150g acetone, then add 7.7g allyl chloride and react at 38℃ for 26h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 1.5g boric acid and 6.5g 4-buten-1-ol, stir evenly, and react at 128℃ until no water vapor is produced to obtain a boron-containing compound. Add 8g of the boron-containing compound to 200g deionized water, stir for 20min, then add 4.1g of the quaternary ammonium salt compound, purge with nitrogen for 10min, then add 0.5g 5wt% hydrogen peroxide aqueous solution and 0.04g ferric chloride, and react at 65℃ for 4h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 3g of aminated Mxene nanosheets to 120g of dimethyl sulfoxide, sonicate for 20min, then add 0.2g of 4-mercaptobenzaldehyde, react at 80℃ for 10h, centrifuge, wash, and dry to obtain modified Mxene nanosheets; mix modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol at a mass ratio of 1:0.2:100, sonicate for 1h, react at 60℃ in a nitrogen atmosphere for 10h, centrifuge, wash, and dry to obtain hybrid inorganic filler; add 3g of hybrid inorganic filler to 120g of ethanol, sonicate for 20min, heat to 60℃, then add 3.6g of binary copolymer and 10g of 0.5wt% azobisisobutyronitrile / ethanol mixed solution, stir and react for 5h, filter, wash, and dry to obtain modified hybrid inorganic filler; Step 3: Add 2.4g of maleic anhydride to 65g of toluene, then add 29.3g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 20℃ for 4.5h, evaporate the solvent to obtain the intermediate product; mix 1.8g of caffeic acid with 5.2g of thionyl chloride, stir for 3h, then react at 76℃ for 30min, distill off excess thionyl chloride to obtain the modifier; add 10g of polypropylene granules to 200g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 40 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.3:0.2 and added to a single-screw extruder. The mixture was extruded at 190°C and 20 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 8 g of surface-modified polypropylene was added to 100 g of N,N-dimethylformamide and sonicated for 20 min. Then, 9.9 g of modifier was added, and the mixture was stirred at room temperature for 12 h. Finally, 28 g of [the modified polypropylene] was added. A 7.5 wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain grafted modified polypropylene. The grafted modified polypropylene was mixed with modified hybrid inorganic filler at a mass ratio of 5:2, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 160℃, zone 2 temperature 165℃, zone 3 temperature 170℃, zone 4 temperature 175℃, zone 5 temperature 180℃, zone 6 temperature 180℃, zone 7 temperature 185℃, zone 8 temperature 190℃, die temperature 190℃, and screw speed 400 rpm.

[0020] Example 4 This embodiment discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 13.4g N,N-dimethylethanolamine and 200g acetone, then add 15.3g allyl chloride and react at 42℃ for 22h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 3.1g boric acid and 12.9g 4-buten-1-ol, stir evenly, and react at 132℃ until no water vapor is produced to obtain a boron-containing compound. Add 16g of the boron-containing compound to 300g deionized water, stir for 30min, then add 8.2g of the quaternary ammonium salt compound, purge with nitrogen for 20min, then add 1.1g 5wt% hydrogen peroxide aqueous solution and 0.06g ferric chloride, and react at 75℃ for 2h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 5g of aminated Mxene nanosheets to 150g of dimethyl sulfoxide and sonicate for 40min. Then add 0.5g of 4-mercaptobenzaldehyde and react at 100℃ for 8h. Centrifuge, wash, and dry to obtain modified Mxene nanosheets. Mix the modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol at a mass ratio of 1:0.4:100, sonicate for 2h, and react at 70℃ for 8h in a nitrogen atmosphere. After the reaction, centrifuge, wash, and dry to obtain hybrid inorganic filler. Add 5g of hybrid inorganic filler to 150g of ethanol and sonicate for 40min. Heat to 70℃, then add 6.4g of binary copolymer and 16g of 0.5wt% azobisisobutyronitrile / ethanol mixed solution. Stir and react for 3h. After the reaction, filter, wash, and dry to obtain modified hybrid inorganic filler. Step 3: Add 4.9g of maleic anhydride to 65g of toluene, then add 58.7g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 24℃ for 3.5h, evaporate the solvent to obtain the intermediate product; mix 3.6g of caffeic acid with 11.8g of thionyl chloride, stir for 4h, then react at 84℃ for 20min, distill off excess thionyl chloride to obtain the modifier; add 10g of polypropylene granules to 200g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 60 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.5:0.2 and added to a single-screw extruder. The mixture was extruded at 200°C and 25 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 10 g of surface-modified polypropylene was added to 150 g of N,N-dimethylformamide and ultrasonically treated for 40 min. Then, 14.9 g of modifier was added, and the mixture was stirred at room temperature for 14 h. Finally, 42 g of [a specific type of modifier] was added. A 7.5wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain grafted modified polypropylene. The grafted modified polypropylene was mixed with modified hybrid inorganic filler at a mass ratio of 9:4.5, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 180℃, zone 2 temperature 185℃, zone 3 temperature 190℃, zone 4 temperature 195℃, zone 5 temperature 200℃, zone 6 temperature 200℃, zone 7 temperature 205℃, zone 8 temperature 210℃, die temperature 210℃, and screw speed 600rpm.

[0021] Example 5 This embodiment discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 10.1g N,N-dimethylethanolamine and 175g acetone, then add 11.5g allyl chloride and react at 40℃ for 24h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 2.3g boric acid and 9.7g 4-buten-1-ol, stir evenly, and react at 130℃ until no water vapor is produced to obtain a boron-containing compound. Add 12g of the boron-containing compound to 250g deionized water, stir for 25min, then add 6.2g of the quaternary ammonium salt compound, purge with nitrogen for 15min, then add 0.8g 5wt% hydrogen peroxide aqueous solution and 0.05g ferric chloride, and react at 70℃ for 3h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 4g of aminated Mxene nanosheets to 135g of dimethyl sulfoxide, sonicate for 30min, then add 0.3g of 4-mercaptobenzaldehyde, react at 90℃ for 9h, centrifuge, wash, and dry to obtain modified Mxene nanosheets; mix modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol at a mass ratio of 1:0.3:100, sonicate for 1.5h, react at 65℃ for 9h in a nitrogen atmosphere, centrifuge, wash, and dry to obtain hybrid inorganic filler; add 4g of hybrid inorganic filler to 135g of ethanol, sonicate for 30min, heat to 65℃, then add 5g of binary copolymer and 13g of 0.5wt% azobisisobutyronitrile / ethanol mixed solution, stir and react for 4h, filter, wash, and dry to obtain modified hybrid inorganic filler; Step 3: Add 3.7g of maleic anhydride to 65g of toluene, then add 44g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 22℃ for 4h, evaporate the solvent to obtain the intermediate product; mix 2.7g of caffeic acid with 8.5g of thionyl chloride, stir for 3.5h, then react at 80℃ for 25min, distill off excess thionyl chloride to obtain the modifier; add 11g of polypropylene granules to 250g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 50 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.4:0.2 and added to a single-screw extruder. The mixture was extruded at 195°C and 22 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 9 g of surface-modified polypropylene was added to 125 g of N,N-dimethylformamide and ultrasonically treated for 30 min. Then, 12.4 g of modifier was added, and the mixture was stirred at room temperature for 13 h. Finally, 35 g of [the following text is missing from the original text and can be omitted] was added. A 7.5 wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain grafted modified polypropylene. The grafted modified polypropylene was mixed with modified hybrid inorganic filler at a mass ratio of 6.5:3.3, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 170℃, zone 2 temperature 175℃, zone 3 temperature 180℃, zone 4 temperature 185℃, zone 5 temperature 190℃, zone 6 temperature 190℃, zone 7 temperature 195℃, zone 8 temperature 200℃, die temperature 200℃, and screw speed 500 rpm.

[0022] Comparative Example 1 This comparative example discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 10.1g N,N-dimethylethanolamine and 175g acetone, then add 11.5g allyl chloride and react at 40℃ for 24h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 2.3g boric acid and 9.7g 4-buten-1-ol, stir evenly, and react at 130℃ until no water vapor is produced to obtain a boron-containing compound. Add 12g of the boron-containing compound to 250g deionized water, stir for 25min, then add 6.2g of the quaternary ammonium salt compound, purge with nitrogen for 15min, then add 0.8g 5wt% hydrogen peroxide aqueous solution and 0.05g ferric chloride, and react at 70℃ for 3h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 4g of aminated Mxene nanosheets to 135g of dimethyl sulfoxide and sonicate for 30min. Then add 0.3g of 4-mercaptobenzaldehyde and react at 90℃ for 9h. Centrifuge, wash, and dry to obtain modified Mxene nanosheets. Add 4g of modified Mxene nanosheets to 135g of ethanol and sonicate for 30min. Heat to 65℃, then add 5g of the binary copolymer and 13g of 0.5wt% azobisisobutyronitrile / ethanol mixed solution. Stir and react for 4h. After the reaction is complete, filter, wash, and dry to obtain the modified inorganic filler. Step 3: Add 3.7g of maleic anhydride to 65g of toluene, then add 44g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 22℃ for 4h, evaporate the solvent to obtain the intermediate product; mix 2.7g of caffeic acid with 8.5g of thionyl chloride, stir for 3.5h, then react at 80℃ for 25min, distill off excess thionyl chloride to obtain the modifier; add 11g of polypropylene granules to 250g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 50 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.4:0.2 and added to a single-screw extruder. The mixture was extruded at 195°C and 22 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 9 g of surface-modified polypropylene was added to 125 g of N,N-dimethylformamide and ultrasonically treated for 30 min. Then, 12.4 g of modifier was added, and the mixture was stirred at room temperature for 13 h. Finally, 35 g of [the following text is missing from the original text and can be omitted] was added. A 7.5 wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain grafted modified polypropylene. The grafted modified polypropylene was mixed with modified inorganic filler at a mass ratio of 6.5:3.3, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 170℃, zone 2 temperature 175℃, zone 3 temperature 180℃, zone 4 temperature 185℃, zone 5 temperature 190℃, zone 6 temperature 190℃, zone 7 temperature 195℃, zone 8 temperature 200℃, die temperature 200℃, and screw speed 500 rpm.

[0023] Comparative Example 2 This comparative example discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 10.1g N,N-dimethylethanolamine and 175g acetone, then add 11.5g allyl chloride and react at 40℃ for 24h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 2.3g boric acid and 9.7g 4-buten-1-ol, stir evenly, and react at 130℃ until no water vapor is produced to obtain a boron-containing compound. Add 12g of the boron-containing compound to 250g deionized water, stir for 25min, then add 6.2g of the quaternary ammonium salt compound, purge with nitrogen for 15min, then add 0.8g 5wt% hydrogen peroxide aqueous solution and 0.05g ferric chloride, and react at 70℃ for 3h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 3.7g of maleic anhydride to 65g of toluene, then add 44g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 22℃ for 4h, evaporate the solvent to obtain the intermediate product; mix 2.7g of caffeic acid with 8.5g of thionyl chloride, stir for 3.5h, then react at 80℃ for 25min, distill off excess thionyl chloride to obtain the modifier; add 11g of polypropylene granules to 250g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 50 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.4:0.2 and added to a single-screw extruder. The mixture was extruded at 195°C and 22 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 9 g of surface-modified polypropylene was added to 125 g of N,N-dimethylformamide and ultrasonically treated for 30 min. Then, 12.4 g of modifier was added, and the mixture was stirred at room temperature for 13 h. Finally, 35 g of [the following text is missing from the original text and can be omitted] was added. A 7.5wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain graft-modified polypropylene. The graft-modified polypropylene was mixed with a binary copolymer at a mass ratio of 6.5:3.3, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 170℃, zone 2 temperature 175℃, zone 3 temperature 180℃, zone 4 temperature 185℃, zone 5 temperature 190℃, zone 6 temperature 190℃, zone 7 temperature 195℃, zone 8 temperature 200℃, die temperature 200℃, and screw speed 500 rpm.

[0024] Comparative Example 3 This comparative example discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Add 4g of aminated Mxene nanosheets to 135g of dimethyl sulfoxide and sonicate for 30min. Then add 0.3g of 4-mercaptobenzaldehyde and react at 90℃ for 9h. Centrifuge, wash, and dry to obtain modified Mxene nanosheets. Mix modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol at a mass ratio of 1:0.3:100, sonicate for 1.5h, and react at 65℃ for 9h in a nitrogen atmosphere. After the reaction is complete, centrifuge, wash, and dry to obtain hybrid inorganic filler. Step 2: Add 3.7g of maleic anhydride to 65g of toluene, then add 44g of a 9.2wt% p-phenylenediamine / diethyl ether mixture, react at 22℃ for 4h, evaporate the solvent to obtain the intermediate product; mix 2.7g of caffeic acid with 8.5g of thionyl chloride, stir for 3.5h, then react at 80℃ for 25min, distill off excess thionyl chloride to obtain the modifier; add 11g of polypropylene granules to 250g of 0.5wt% p-phenylenediamine / diethyl ether mixture. In a mixture of 2,6-di-tert-butyl-p-cresol and acetone, the mixture was stirred for 50 min and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:0.4:0.2 and added to a single-screw extruder. The mixture was extruded at 195°C and 22 rpm. The resulting solid was added to boiling xylene, and the product was precipitated with acetone. The product was filtered, washed, and dried to obtain surface-modified polypropylene. 9 g of surface-modified polypropylene was added to 125 g of N,N-dimethylformamide and ultrasonically treated for 30 min. Then, 12.4 g of modifier was added, and the mixture was stirred at room temperature for 13 h. Finally, 35 g of [the following text is missing from the original text and can be omitted] was added. A 7.5 wt% sodium bicarbonate aqueous solution was filtered, the precipitate was collected, and dried to obtain grafted modified polypropylene. The grafted modified polypropylene was mixed with hybrid inorganic filler at a mass ratio of 6.5:3.3, and then extruded and granulated using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder were as follows: zone 1 temperature 170℃, zone 2 temperature 175℃, zone 3 temperature 180℃, zone 4 temperature 185℃, zone 5 temperature 190℃, zone 6 temperature 190℃, zone 7 temperature 195℃, zone 8 temperature 200℃, die temperature 200℃, and screw speed 500 rpm.

[0025] Comparative Example 4 This comparative example discloses a method for preparing antistatic polypropylene masterbatch, the specific steps of which are as follows: Step 1: Mix 10.1g N,N-dimethylethanolamine and 175g acetone, then add 11.5g allyl chloride and react at 40℃ for 24h. After the reaction, wash the product repeatedly with acetone, dry, and grind to obtain a quaternary ammonium salt compound. Mix 2.3g boric acid and 9.7g 4-buten-1-ol, stir evenly, and react at 130℃ until no water vapor is produced to obtain a boron-containing compound. Add 12g of the boron-containing compound to 250g deionized water, stir for 25min, then add 6.2g of the quaternary ammonium salt compound, purge with nitrogen for 15min, then add 0.8g 5wt% hydrogen peroxide aqueous solution and 0.05g ferric chloride, and react at 70℃ for 3h. After the reaction, evaporate the solvent to obtain a binary copolymer. Step 2: Add 4g of aminated Mxene nanosheets to 135g of dimethyl sulfoxide, sonicate for 30min, then add 0.3g of 4-mercaptobenzaldehyde, react at 90℃ for 9h, centrifuge, wash, and dry to obtain modified Mxene nanosheets; mix modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol at a mass ratio of 1:0.3:100, sonicate for 1.5h, react at 65℃ for 9h in a nitrogen atmosphere, centrifuge, wash, and dry to obtain hybrid inorganic filler; add 4g of hybrid inorganic filler to 135g of ethanol, sonicate for 30min, heat to 65℃, then add 5g of binary copolymer and 13g of 0.5wt% azobisisobutyronitrile / ethanol mixed solution, stir and react for 4h, filter, wash, and dry to obtain modified hybrid inorganic filler; Step 3: Mix polypropylene granules with modified hybrid inorganic fillers at a mass ratio of 6.5:3.3, and then extrude and granulate the mixture using a twin-screw extruder to obtain antistatic polypropylene masterbatch. The extrusion process parameters of the twin-screw extruder are as follows: Zone 1 temperature 170℃, Zone 2 temperature 175℃, Zone 3 temperature 180℃, Zone 4 temperature 185℃, Zone 5 temperature 190℃, Zone 6 temperature 190℃, Zone 7 temperature 195℃, Zone 8 temperature 200℃, Die temperature 200℃, and Screw speed 500 rpm.

[0026] The aminated Mxene nanosheets and modified ultrafine Ce-MOF nanorods used in Examples 3-5 and Comparative Examples 1 and 3-4 are the aminated Mxene nanosheets prepared in Example 1 and the modified ultrafine Ce-MOF nanorods prepared in Example 2.

[0027] In the above examples and comparative examples, the polypropylene particles, grade: PPH-T03, melt index: 2.5 g / 10 min, brand: Sinopec, came from Guangzhou Jiushun New Materials Co., Ltd.; the MAX phase Ti3AlC2 powder, with a particle size of 1-10 μm, came from Qinghe County Yaoxie Metal Materials Co., Ltd.

[0028] Experimental Example The antistatic polypropylene masterbatches prepared in Examples 3-5 and Comparative Examples 1-4 were melt-spun to obtain polypropylene fibers. The melt-spinning process was as follows: spinning temperature 240℃, draw ratio 4, and spinning speed 800m / min. The polypropylene fibers in each group were sequentially labeled as Sample 3, Sample 4, Sample 5, Comparative Sample 1, Comparative Sample 2, Comparative Sample 3, and Comparative Sample 4. Performance tests were performed on each group of samples.

[0029] I. Antistatic performance test: The resistivity of each group of samples was tested in accordance with the standard GB / T 12703.4-2010 "Evaluation of electrostatic properties of textiles - Part 4: Resistivity".

[0030] II. Antibacterial performance test: Refer to standard GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method", and select Staphylococcus aureus and Escherichia coli as bacterial strains.

[0031] III. Flame retardant performance test: The oxygen index of each group of samples was tested in accordance with the standard GB / T 5454-2022 "Test for flammability of textiles - Oxygen Index Method".

[0032] IV. Moisture absorption performance test: The moisture regain of each group of samples was tested in accordance with the standard GB / T 6503-2008 "Test method for moisture regain of chemical fibers".

[0033] The test results are shown in Table 1:

[0034] As shown in Table 1, the polypropylene masterbatches prepared in Examples 3-5 of this invention exhibit excellent antibacterial, hygroscopic, antistatic, and flame-retardant properties. A comparison between samples 1-2 and sample 5 reveals that ultrafine Ce-MOF nanorods possess flame-retardant and conductive properties. Modification with dimethyl phosphate further improves the flame-retardant properties of the ultrafine Ce-MOF nanorods. Mxene nanosheets possess flame-retardant, conductive, and hydrophilic hygroscopic properties. Modified ultrafine Ce-MOF nanorods can serve as bridging points for Mxene nanosheets, forming a complex conductive network, enhancing conductivity, and imparting antistatic properties to polypropylene fibers. Furthermore, the modified ultrafine Ce-MOF nanorods and modified Mxene nanosheets can synergistically enhance flame retardancy, thereby improving the flame-retardant properties of polypropylene fibers. A comparison between samples 3 and 5 shows that the presence of hydrophilic / antibacterial quaternary ammonium salt structures, hydrophilic hydroxyl groups, and flame-retardant boron elements in the binary copolymer improves the hydrophilic hygroscopic and antistatic properties of the hybrid inorganic filler. The product exhibits antibacterial and flame-retardant properties. Simultaneously, the organic chains of the binary copolymer crosslink with polypropylene and form hydrogen bonds with the grafted modified polypropylene, improving the dispersibility of the hybrid inorganic filler and increasing the crosslinking density of the polypropylene system. While maintaining the mechanical properties of the polypropylene matrix, it enhances antibacterial, hygroscopic, antistatic, and flame-retardant properties. A comparison between sample 4 and sample 5 shows that the introduction of abundant amino groups on the polypropylene surface provides reactive groups and improves the hygroscopic permeability and antistatic properties of polypropylene. Furthermore, grafting caffeic acid structures onto the polypropylene branches introduces catechol structures, endowing polypropylene with antibacterial properties and further improving its hygroscopic and antistatic properties. In addition, graft modification of polypropylene improves the dispersibility of the modified hybrid inorganic filler, thereby enhancing the overall performance of the polypropylene fiber.

[0035] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing antistatic polypropylene masterbatch, characterized in that, Includes the following steps: Step 1: The boron-containing compound and the quaternary ammonium salt compound are polymerized to obtain a binary copolymer; Step 2: Combine modified Mxene nanosheets with modified ultrafine Ce-MOF nanorods to obtain hybrid inorganic fillers; react the hybrid inorganic fillers with binary copolymers to obtain modified hybrid inorganic fillers. Step 3: Maleic anhydride reacts with p-phenylenediamine to obtain an intermediate product; pretreated polypropylene, the intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane are mixed and extruded to obtain surface-modified polypropylene. Surface-modified polypropylene is modified with a modifier to obtain graft-modified polypropylene; the graft-modified polypropylene is mixed with modified hybrid inorganic filler, extruded and granulated to obtain antistatic polypropylene masterbatch.

2. The method for preparing antistatic polypropylene masterbatch according to claim 1, characterized in that, In step one, the preparation method of the binary copolymer specifically includes: weighing N,N-dimethylethanolamine, acetone, and allyl chloride in a mass ratio of (6.8-13.4):(150-200):(7.7-15.3), reacting at 38-42℃ for 22-26 h, purifying, and obtaining a quaternary ammonium salt compound; mixing boric acid and 4-buten-1-ol in a mass ratio of (1.5-3.1):(6.5-12.9), reacting at 128-132℃, and obtaining a boron-containing compound. Compound; add boron-containing compound to deionized water, stir, then add quaternary ammonium salt compound, purge with nitrogen, then add 5wt% hydrogen peroxide aqueous solution and ferric chloride, react at 65-75℃ for 2-4h, purify, and obtain binary copolymer; wherein, the mass ratio of boron-containing compound, deionized water, quaternary ammonium salt compound, 5wt% hydrogen peroxide aqueous solution and ferric chloride is (8-16):(200-300):(4.1-8.2):(0.5-1.1):(0.04-0.06).

3. The method for preparing antistatic polypropylene masterbatch according to claim 1, characterized in that, In step two, the preparation method of the modified hybrid inorganic filler specifically includes: weighing aminated Mxene nanosheets, dimethyl sulfoxide, and 4-mercaptobenzaldehyde in a mass ratio of (3-5):(120-150):(0.2-0.5), reacting at 80-100℃ for 8-10 h, purifying, and obtaining modified Mxene nanosheets; mixing the modified Mxene nanosheets, modified ultrafine Ce-MOF nanorods, and ethanol in a mass ratio of 1:(0.2-0.4):100, sonicating, and then in a nitrogen atmosphere. The mixture was reacted at 60-70℃ for 8-10 hours, purified, and the hybrid inorganic filler was obtained. The hybrid inorganic filler was added to ethanol, sonicated, heated to 60-70℃, and then the binary copolymer and 0.5wt% azobisisobutyronitrile / ethanol mixed solution were added. The mixture was stirred and reacted for 3-5 hours, purified, and the modified hybrid inorganic filler was obtained. The mass ratio of the hybrid inorganic filler, ethanol, binary copolymer, and 0.5wt% azobisisobutyronitrile / ethanol mixed solution was (3-5):(120-150):(3.6-6.4):(10-16).

4. The method for preparing antistatic polypropylene masterbatch according to claim 3, characterized in that, The aminated Mxene nanosheets are prepared by the following steps: Step A1: Mix MAX phase Ti3AlC2 powder, lithium fluoride, and 9 mol / L hydrochloric acid aqueous solution at a mass ratio of (2-4):(2-4):(19-38), stir at 36-40℃ for 40-50 h, centrifuge, wash, add the washed precipitate to deionized water, sonicate in a nitrogen atmosphere for 50-70 min, centrifuge, freeze dry to obtain Mxene nanosheets; mix Mxene nanosheets and dimethyl sulfoxide at a mass ratio of (1-3):(50-80), sonicate for 20-40 min, stir in a nitrogen atmosphere for 45-50 h, purify to obtain hydroxylated Mxene nanosheets; Step A2: Mix silane coupling agent KH-550 and ethanol / water mixture at a mass ratio of (1-3):41, adjust pH to 4.5, and pre-hydrolyze for 2 hours to obtain silane coupling agent KH-550 hydrolysate; mix hydroxylated Mxene nanosheets and ethanol / water mixture at a mass ratio of (3-5):41, sonicate, then add the above silane coupling agent KH-550 hydrolysate, stir and react for 6-8 hours in a nitrogen atmosphere at 28-32℃, purify, and obtain aminolated Mxene nanosheets.

5. The method for preparing antistatic polypropylene masterbatch according to claim 3, characterized in that, The modified ultrafine Ce-MOF nanorods are prepared by the following steps: Step B1: Sodium hydroxide, trimesic acid, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are mixed in a ratio of (0.04-0.08) g : (0.07-0.14) g : (3-6) g : (60-120) mL : (2-4) mL, and vortexed for 30 s to obtain the ligand micelle phase; cerium nitrate hexahydrate, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are mixed in a ratio of (0.04-0.08) g : (0.07-0.14) g : (3-6) g : (60-120) mL : (2-4) mL, and the mixture is vortexed for 30 s to obtain the ligand micelle phase; cerium nitrate hexahydrate, water, a 0.1 mol / L sodium dodecyl sulfate aqueous solution, and a 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution are .... A 0.1 mol / L hexadecyltrimethylammonium bromide aqueous solution was mixed at a ratio of (0.14-0.28) g: (2-4) g: (40-80) mL: (1-2) mL, sonicated, and the above ligand micelle phase was added dropwise over 1 hour. The mixture was reacted at 38-42℃ for 2.5-3.5 hours, followed by the addition of 30 wt% hydrogen peroxide aqueous solution and the reaction at 24-26℃ for 50-70 minutes. After purification, ultrafine Ce-MOF nanorods with an average diameter of 50 nm were obtained. Step B2: Mix ultrafine Ce-MOF nanorods, ethanol, and a 0.002 g / mL dimethyl phosphate / ethanol mixture at a mass ratio of (1-3):(80-100):(80-120), stir and react at 58-62℃ for 50-70 min, and purify to obtain modified ultrafine Ce-MOF nanorods.

6. The method for preparing antistatic polypropylene masterbatch according to claim 1, characterized in that, In step three, the preparation method of the surface-modified polypropylene specifically includes: adding maleic anhydride to toluene, adding a 9.2wt% p-phenylenediamine / ethyl ether mixture, reacting at 20-24℃ for 3.5-4.5h, evaporating the solvent to obtain an intermediate product; wherein the mass ratio of maleic anhydride, toluene, and 9.2wt% p-phenylenediamine / ethyl ether mixture is (2.4-4.9):65:(29.3-58.7); mixing caffeic acid and thionyl chloride at a mass ratio of (1.8-3.6):(5.2-11.8), stirring, reacting at 76-84℃ for 20-30min, distilling to obtain the modifier; and mixing polypropylene particles with 0.5wt% p-phenylenediamine / ethyl ether mixture. A mixture of 2,6-di-tert-butyl-p-cresol and acetone was mixed at a mass ratio of (10-12):(200-300), stirred for 40-60 min, and then rotary evaporated to obtain pretreated polypropylene. The pretreated polypropylene, intermediate product, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane were mixed at a mass ratio of 100:(0.3-0.5):0.2, extruded at 190-200℃ and 20-25 rpm, and purified to obtain surface-modified polypropylene.

7. The method for preparing antistatic polypropylene masterbatch according to claim 1, characterized in that, In step three, the preparation method of the grafted modified polypropylene specifically includes: adding surface-modified polypropylene to N,N-dimethylformamide, sonicating, then adding a modifier, stirring and reacting at room temperature for 12-14 hours, purifying, and obtaining grafted modified polypropylene; wherein, the mass ratio of surface-modified polypropylene, N,N-dimethylformamide, and modifier is (8-10):(100-150):(9.9-14.9).

8. The method for preparing antistatic polypropylene masterbatch according to claim 1, characterized in that, In step three, the mass ratio of the grafted modified polypropylene to the modified hybrid inorganic filler is (5-9):(2-4.5); the extrusion process parameters are: zone 1 temperature 160-180℃, zone 2 temperature 165-185℃, zone 3 temperature 170-190℃, zone 4 temperature 175-195℃, zone 5 temperature 180-200℃, zone 6 temperature 180-200℃, zone 7 temperature 185-205℃, zone 8 temperature 190-210℃, die temperature 190-210℃, and screw speed 400-600rpm.

9. An antistatic polypropylene masterbatch prepared by the method for preparing antistatic polypropylene masterbatch tape as described in any one of claims 1-8.

10. The application of the antistatic polypropylene masterbatch according to claim 9 in polypropylene fiber.

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