Wear-resistant antistatic polyethylene material and preparation method thereof

Abstract

The invention discloses a wear-resistant antistatic polyethylene material and a preparation method thereof, and relates to the technical field of polyethylene composites.The preparation method comprises the following steps that high-density polyethylene, low-density polyethylene, linear low-density polyethylene, butadiene rubber, filler and auxiliaries are mixed and extruded, and a polyethylene material is obtained; wherein butadiene rubber is hydrogenated after being modified by an alkenyl compound. The polyethylene material is prepared by mixing polyethylene of various specifications with butadiene rubber and filler, so that the polyethylene material has good comprehensive performance; the butadiene rubber is modified by norbornene quaternary ammonium salt, cyclooctene and maleamido disiloxane, so that the mechanical properties, wear resistance and antistatic capability of the modified butadiene rubber and the polyethylene material prepared from the modified butadiene rubber are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polyethylene composite materials, and specifically relates to a wear-resistant and antistatic polyethylene material and a preparation method thereof. Background Art

[0002] Due to its light weight, durability, easy processing and other characteristics, plastic barrels are widely used in modern industrial production and daily life. Plastic molding devices are often used in various fields such as material storage and transportation in daily life and industrial production. Blow molding container factories use high-density polyethylene (HDPE) as raw materials. Its molecular weight is relatively high, which can meet the strength requirements of products, and has good fluidity and toughness, and is suitable as a material for material storage and transportation. In the actual application environment, there are some environments that require frequent use and bear friction, which poses a test to the wear resistance of the material, and its wear resistance directly affects the service life and performance of plastic parts. And plastics will generate static electricity during the friction process. With the accumulation of static electricity, spark discharge may be triggered, leading to accidents. Therefore, we propose a wear-resistant and antistatic polyethylene material and a preparation method thereof. Summary of the Invention

[0003] The purpose of the present invention is to provide a wear-resistant and antistatic polyethylene material and a preparation method thereof to solve the problems raised in the above background art.

[0004] To solve the above technical problems, the present invention provides the following technical solutions: A wear-resistant and antistatic polyethylene material, comprising the following components: 70-85 parts of high-density polyethylene (HDPE), 10-15 parts of low-density polyethylene (LDPE), 3-5 parts of linear low-density polyethylene (LLDPE), 8-15 parts of cis-1,4-polybutadiene rubber, 10-20 parts of filler, 2-9 parts of additives.

[0005] Further, the filler is one or more mixtures of silica, silicon nitride, talcum powder, calcium carbonate, diatomite, wollastonite;

[0006] The particle size of the filler is 800-1250 mesh.

[0007] Further, the additives include 0.1-5 parts of antistatic agent, 1-3 parts of compatibilizer, 0.1-0.3 parts of antioxidant, 0.2-0.6 parts of light stabilizer, 0.2-1.0 parts of lubricant;

[0008] The antistatic agent is one or more composites of Armostat600, Armostat400, IrgastatP18, IrgastatP22, PebaxMH1657, Stat-RiteC-2300, antistatic agent SN.

[0009] The compatibilizer is one or a mixture of more than one of MAH-g-PE (maleic anhydride grafted polyethylene), SEBS-g-MAH (maleic anhydride grafted hydrogenated styrene-butadiene-styrene block copolymer), and EMA (ethylene-acrylate copolymer);

[0010] The antioxidant is one or a mixture of two of antioxidant 1010 and antioxidant 168;

[0011] The light stabilizer is one or a mixture of more than one of Tinuvin770, Chimassorb944, Tinuvin326, and CyasorbUV-531;

[0012] The lubricant is one or a mixture of more than one of stearic acid, stearate, ethylene bisstearamide, aliphatic hydrocarbon wax, polyethylene wax, and oxidized polyethylene.

[0013] Furthermore, the antistatic agent is Stat-RiteC-2300 and Armostat600, and the mass ratio is 4.4:1;

[0014] The compatibilizer is MAH-g-PE;

[0015] The antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio is 2:1;

[0016] The light stabilizer is a mixture of Tinuvin770 and Tinuvin326, and the mass ratio is 2:1;

[0017] The lubricant is polyethylene wax.

[0018] In the above technical solution, high-density polyethylene (HDPE) is used as the main resin matrix, supplemented with low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), cis-1,4-polybutadiene rubber (BR), and filler, and a polyethylene material is prepared by coextrusion. High-density polyethylene has good mechanical strength and can provide properties such as rigidity, strength, and chemical resistance for the polyethylene material. An appropriate content of HDPE can improve the hardness, impact resistance, and pressure resistance of the polyethylene material; while too high a content of HDPE will reduce the flexibility of the polyethylene material, increase brittleness, and make it more prone to low-temperature cracking; too low a content of HDPE will lead to a decrease in the rigidity of the polyethylene material and the polyethylene material is prone to deformation.

[0019] Low-density polyethylene (LDPE) can improve the processing fluidity, flexibility, and surface gloss of the polyethylene material. An appropriate content of LDPE can improve its melt strength, improve processing stability, enhance the fold resistance and low-temperature toughness of the polyethylene material while maintaining good rigidity of the polyethylene material. Too high or too low a content of LDPE will reduce the rigidity of the polyethylene material and deteriorate its processing fluidity.

[0020] Linear low density polyethylene (LLDPE) can enhance the mechanical properties, tear resistance, puncture resistance, heat resistance, etc. of polyethylene materials. An appropriate content of LLDPE can improve the impact resistance and puncture resistance of polyethylene materials while maintaining the rigidity advantage of HDPE. However, too low or too high a content of LLDPE will reduce the tear resistance or transparency of polyethylene materials.

[0021] The molecular structure of cis-1,4-polybutadiene rubber (BR) is highly regular, endowing it with excellent elasticity, abrasion resistance and low temperature resistance, and its cold resistance is excellent. The addition of BR can significantly improve the elasticity, cold resistance and abrasion resistance of polyethylene materials, improve their resistance to low temperature impact, enhance their mechanical properties and environmental stress cracking resistance, and improve the comprehensive properties of polyethylene materials. An appropriate content of BR can maintain the high rigidity of polyethylene materials, provide high elastic buffering, improve their low temperature toughness, and reduce their risk of falling and breaking. However, too low or too high a content of BR will increase its low temperature brittleness or reduce its hardness and increase the risk of deformation. The compatibilizer added in the additives can improve the compatibility between cis-1,4-polybutadiene rubber and polyethylene, enhance the interaction between the two, and improve the stability of the prepared polyethylene materials.

[0022] The increase of fillers can improve the rigidity and dimensional stability of polyethylene materials while maintaining good strength and toughness. However, too low or too high a content of fillers will affect the stability of polyethylene materials, resulting in a decrease in toughness and deterioration of processing fluidity.

[0023] A preparation method of wear-resistant and antistatic polyethylene material includes the following processes:

[0024] Mix high density polyethylene, low density polyethylene, linear low density polyethylene, cis-1,4-polybutadiene rubber, fillers and additives, and extrude to obtain polyethylene materials.

[0025] Further, the process conditions of the mixing are as follows:

[0026] Premix high density polyethylene, low density polyethylene, linear low density polyethylene at 80 - 100 °C for 5 - 8 min;

[0027] Add compatibilizer and fillers, raise the temperature to 100 - 120 °C, and mix for 8 - 12 min;

[0028] Cool down to 75 - 80 °C, add antioxidant and light stabilizer, mix for 5 - 7 min, add Stat-RiteC-2300, and continue to mix for 4 - 6 min;

[0029] Add cis-1,4-polybutadiene rubber and Armostat600, and continue to mix at 60 - 80 °C for 4 - 6 min; finally add lubricant and mix for 2 - 4 min to obtain the premix.

[0030] Further, the process conditions for extrusion are as follows: in a twin-screw extruder, plasticize by extrusion and pelletize to form polyethylene pellets. The temperatures of each zone of the extruder are successively: zone 1 at 160 - 180°C, zone 2 at 180 - 200°C, zone 3 at 190 - 210°C, zone 4 at 180 - 200°C, the die head temperature at 170 - 190°C, and the rotation speed at 200 - 400 rpm.

[0031] Further, underwater pelletizing at 20 - 40°C or air-cooled strand pelletizing is used for pelletizing.

[0032] Further, after underwater pelletizing, the polyethylene pellets are centrifugally dehydrated and dried with hot air at 60 ± 2°C.

[0033] Further, when the polyethylene material is applied, it is blow-molded in a blow molding machine for hollow extrusion. The temperatures of each zone are successively: zone 1 at 160 - 170°C, zone 2 at 180 - 190°C, zone 3 at 190 - 200°C, the head at 190 - 200°C, and the rotation speed at 40 - 60 rpm;

[0034] The blowing pressure is 0.4 - 0.8 MPa, the blowing time is 3 - 8 seconds, the mold temperature is 20 - 50°C, and the cooling time is 15 - 30 seconds.

[0035] Further, the cis-1,4-polybutadiene rubber is subjected to a modification treatment, and the specific process is as follows:

[0036] Dry the cis-1,4-polybutadiene rubber and the vinyl compound, mix them, dissolve them in tetrahydrofuran under the protection of a nitrogen atmosphere, add a catalyst, and react at a temperature of 40 - 45°C for 30 - 60 min; end the reaction with anhydrous methanol, perform rotary evaporation, precipitate the catalyst with n-hexane, filter, perform rotary evaporation, and vacuum dry to obtain the modified cis-1,4-polybutadiene rubber; hydrogenate to obtain the hydrogenated cis-1,4-polybutadiene rubber.

[0037] Further, the mass ratio of the cis-1,4-polybutadiene rubber to the vinyl compound is 10:(1 - 2).

[0038] Further, the vinyl compound is a mixture of a norbornenyl quaternary ammonium salt, cyclooctene, and maleamido disiloxane, and the mass ratio is (0.1 - 0.5):(0.5 - 1.2):(0.3 - 0.8).

[0039] Further, the ratio of the cis-1,4-polybutadiene rubber to tetrahydrofuran is (3 - 8) g / 100 mL.

[0040] Further, the catalyst is a Grubbs II generation catalyst, and the dosage is 0.05 - 0.30 wt% of the mass of the cis-1,4-polybutadiene rubber.

[0041] Further, the hydrogenation process is as follows:

[0042] Mix the modified cis - 1,4 - polybutadiene rubber and p - toluenesulfonyl hydrazide, add o - xylene for dissolution in a nitrogen atmosphere, add tri - n - propylamine, and react at a temperature of 133 - 137 °C for 225 - 250 min; perform rotary evaporation, precipitate with ethanol, filter, wash, and dry to obtain hydrogenated cis - 1,4 - polybutadiene rubber.

[0043] Furthermore, the mass ratio of the modified cis - 1,4 - polybutadiene rubber, p - toluenesulfonyl hydrazide, and tri - n - propylamine is 10:(2 - 3):(0.6 - 1.5);

[0044] The ratio of the modified cis - 1,4 - polybutadiene rubber to o - xylene is 10 g / 100 mL.

[0045] In the above - mentioned technical solution, using maleamide - based disiloxane as a symmetric chain - transfer agent, norbornenyl quaternary ammonium salt and cyclooctene as monomers, under the action of a catalyst, polyolefins are formed through ring - opening metathesis polymerization / cross - metathesis. At the same time, the catalyst can activate the carbon - carbon double bonds in cis - 1,4 - polybutadiene rubber, undergo olefin metathesis degradation, and participate in the above - mentioned polymerization reaction to form polyolefin - modified cis - 1,4 - polybutadiene rubber, denoted as modified cis - 1,4 - polybutadiene rubber; then hydrogenation is carried out to obtain hydrogenated cis - 1,4 - polybutadiene rubber.

[0046] The introduced norbornenyl quaternary ammonium salt has a rigid cyclic structure of norbornenyl, which enhances the rigidity of the molecular chain of hydrogenated cis - 1,4 - polybutadiene rubber, can improve the mechanical properties of the prepared polyethylene material, and to a certain extent, improve its wear - resistance. The quaternary ammonium salt group has a cation and a mobile anion, which can neutralize the accumulated static charges, assist charge transfer through molecular chain swing / local Brownian motion, and realize the improvement of the antistatic performance of the polyethylene material. At the same time, the quaternary ammonium salt cation can participate in ionic cross - linking, form reversible ionic bonds with electronegative groups such as COO - and OH - in the polyethylene material system, enhance its mechanical properties, provide charge - hopping sites, and further enhance the wear - resistance of the polyethylene material, improving durability. The ring - opening polymerization of cyclooctene and its modification of cis - 1,4 - polybutadiene rubber can enhance the entanglement between molecular chains in the polyethylene material, resist shear damage caused by wear, hinder the sliding of molecular chains during friction, reduce adhesive wear on the surface of the polyethylene material, and improve the wear - resistance of the polyethylene material. And it helps to improve the mechanical properties and maintain the low - temperature toughness of the polyethylene material. Maleamide - based disiloxane introduces silicone segments into the cis - 1,4 - polybutadiene rubber and the prepared polyethylene material system, which helps to improve its tensile strength, wear - resistance, and thermal properties; and can reduce its flow resistance and improve processing performance.

[0047] After hydrogenation, the unsaturated double bonds in cis - 1,4 - polybutadiene rubber are reduced to saturated bonds, and the mechanical properties of the prepared hydrogenated cis - 1,4 - polybutadiene rubber are significantly improved, with better wear - resistance, and its heat - resistance, aging - resistance, and chemical stability are improved. It can maintain stability at higher temperatures and during long - term use, increase the resistance to erosion by various chemical media, and extend the service life of the prepared polyethylene material.

[0048] Furthermore, the norbornenyl quaternary ammonium salt is prepared by the following process:

[0049] Mix norbornene dianhydride and 3-dimethylaminopropylamine in toluene and reflux for 24 h to obtain dimethylaminopropyl norbornene;

[0050] Mix dimethylaminopropyl norbornene and lithium aluminum hydride in anhydrous ether and dichloromethane, stir and react for 24 h; add methyl iodide and stir for 12 h; filter, distill under reduced pressure, wash and dry to obtain the norbornenyl quaternary ammonium salt.

[0051] Furthermore, the molar ratio of norbornene dianhydride, 3-dimethylaminopropylamine, lithium aluminum hydride and methyl iodide is 1:(1.2 - 1.5):(0.25 - 0.30):(2.0 - 2.2).

[0052] Furthermore, the ratio of norbornene dianhydride to toluene is 10 g:(3 - 5) mL;

[0053] The ratio of dimethylaminopropyl norbornene, anhydrous ether and dichloromethane is 10 g:(20 - 40) mL:(60 - 80) mL.

[0054] In the above technical solution, norbornene dianhydride and 3-dimethylaminopropylamine are mixed and reacted to form dimethylaminopropyl norbornene, and then quaternization is carried out to form a norbornenyl quaternary ammonium salt with two quaternary ammonium salt functional groups, which helps to increase the number of cations in hydrogenated cis-1,4-polybutadiene rubber and further improve the wear resistance, mechanical properties and antistatic ability of the prepared polyethylene material.

[0055] Furthermore, the maleamido disiloxane is prepared by the following process:

[0056] Mix amino siloxane, catalyst and anhydrous toluene, slowly add maleic anhydride under the protection of nitrogen atmosphere, finish adding within 30 min, heat to 25 - 50 °C and react for 2 - 6 h; raise the temperature to 85 - 93 °C and continue to react for 3 - 4 h;

[0057] Cool to 60 °C, add 5% sodium bicarbonate for washing, separate the liquid, take the organic layer for drying, distill under reduced pressure, chromatograph and vacuum dry to obtain maleamido disiloxane.

[0058] Furthermore, the molar ratio of amino siloxane to maleic anhydride is (2.2 - 2.5):1.

[0059] Furthermore, the catalyst is triethylamine and its dosage is 1 - 3 mol% of amino siloxane.

[0060] Further, the ratio of amino silicone to anhydrous toluene is 10 g : (3 - 5) mL.

[0061] Further, in the preparation process of maleamide disiloxane, reflux and water separation are carried out during the reaction; and the pH of the reaction system is maintained at ≤ 5.

[0062] Further, in the preparation process of maleamide disiloxane, 0.1 - 0.5 wt% of butylated hydroxytoluene is added (relative to the total mass of amino silicone and maleic anhydride).

[0063] Further, the amino silicone is one of N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysiloxane.

[0064] In the above technical solution, maleic anhydride reacts with amino silicone to form a maleamide compound with a symmetric siloxane segment, denoted as maleamide disiloxane, which is suitable as a symmetric chain transfer agent to participate in the modification of cis-1,4-polybutadiene rubber and introduce amide groups and siloxane segments.

[0065] When the amino silicone is selected as N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, or 3-aminopropyltriethoxysiloxane, hydrogenated rubber is mixed with the filler to achieve the coating of the filler by hydrogenated cis-1,4-polybutadiene rubber, which helps the dispersion of the filler in the polyethylene material and ensures the full play of the properties of materials such as the filler.

[0066] Further, in the mixing process, the filler and the modified cis-1,4-polybutadiene rubber are added together and pre-mixed before addition. The pre-mixing process is as follows:

[0067] Place the hydrogenated cis-1,4-polybutadiene rubber in an internal mixer and plastify for 2 - 3 min; add the filler in three portions at intervals of 1 min, then mix at 50 - 70 °C for 6 - 12 min at a rotational speed of 40 - 60 rpm and a pressure of 0.5 - 0.8 MPa; then transfer to an open mill and thin-pass 3 - 5 times at 40 - 50 °C, take off the sheet and cool, cut into pellets to obtain the filler / hydrogenated cis-1,4-polybutadiene rubber mixture.

[0068] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0069] 1. A wear-resistant and antistatic polyethylene material and its preparation method disclosed by the present invention. The present invention prepares a polyethylene material by mixing polyethylene of various specifications with cis-1,4-polybutadiene rubber and a filler, making it have good comprehensive properties.

[0070] 2. A wear-resistant and antistatic polyethylene material and its preparation method disclosed by the present invention modify cis-butadiene rubber with norbornenyl quaternary ammonium salt, cyclooctene, and maleamide-based disiloxane, improving the mechanical properties, wear resistance, and antistatic ability of the modified cis-butadiene rubber and the polyethylene material prepared therefrom. Detailed implementation mode

[0071] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0072] In the following detailed implementation modes:

[0073] The antistatic agents are Stat-Rite C-2300 and Armostat 600, and the mass ratio is 4.4:1;

[0074] The compatibilizer is MAH-g-PE;

[0075] The antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio is 2:1;

[0076] The light stabilizer is a mixture of Tinuvin 770 and Tinuvin 326, and the mass ratio is 2:1;

[0077] The lubricant is polyethylene wax;

[0078] High-density polyethylene: DMDA-8008 from Dushanzi Petrochemical of CNPC;

[0079] Low-density polyethylene: LD450 from Yanshan Petrochemical;

[0080] Linear low-density polyethylene: 4023WN from SABIC of Saudi Arabia,

[0081] Cis-butadiene rubber: BR9003 from Yanshan Petrochemical;

[0082] The filler is silica, and the particle size is 1000 mesh; the filler is surface-treated before addition. The surface treatment process is as follows: The filler is dried at 110 °C for 4 h, dispersed in 20% ethanol, 3 wt% coupling agent KH-550 (relative to the mass of the filler) is added, stirred at 80 °C for 2 h, filtered, dried at 100 °C, and sieved through a 1000-mesh sieve to obtain; the ratio of the filler to ethanol is 30 g / 100 mL;

[0083] In Examples 1-3, in the preparation process of maleamide-based disiloxane, water was refluxed and separated during the reaction; and the pH of the reaction system was maintained at 4.5 ± 0.2; in the preparation process of maleamide-based disiloxane, 0.3 wt% of butylhydroxytoluene (relative to the total mass of amino siloxane and maleic anhydride) was added.

[0084] Example 1: A method for preparing a wear-resistant and antistatic polyethylene material, comprising the following processes:

[0085] Step 1: Mix norbornene dicarboxylic anhydride and 3-dimethylaminopropylamine in toluene and reflux for 24 h to obtain dimethylaminopropyl norbornene; mix dimethylaminopropyl norbornene and lithium aluminum hydride in anhydrous ether and dichloromethane, stir and react for 24 h; add methyl iodide and stir for 12 h; filter, distill under reduced pressure, wash, and dry to obtain norbornene-based quaternary ammonium salt; the molar ratio of norbornene dicarboxylic anhydride, 3-dimethylaminopropylamine, lithium aluminum hydride, and methyl iodide is 1:1.2:0.25:2.0; the ratio of norbornene dicarboxylic anhydride to toluene is 10 g:3 mL; the ratio of dimethylaminopropyl norbornene, anhydrous ether, and dichloromethane is 10 g:20 mL:80 mL;

[0086] Mix amino siloxane, 1 mol% of triethylamine catalyst, and anhydrous toluene, and slowly add maleic anhydride under the protection of a nitrogen atmosphere within 30 min, heat to 25 °C, and react for 6 h; raise the temperature to 85 °C and continue to react for 4 h; cool to 60 °C, add 5% sodium bicarbonate for washing, separate the layers, take the organic layer for drying, distill under reduced pressure, chromatograph, and vacuum dry to obtain maleamide-based disiloxane; the molar ratio of amino siloxane to maleic anhydride is 2.2:1; the ratio of amino siloxane to anhydrous toluene is 10 g:3 mL; the amino siloxane is 3-aminopropyltrimethoxysilane;

[0087] Dry the cis-1,4-polybutadiene and the alkenyl compound, mix them, dissolve them in tetrahydrofuran under the protection of a nitrogen atmosphere, add 0.05 wt% of the Grubbs II generation catalyst, and react at 40 °C for 30 min; terminate the reaction with anhydrous methanol, perform rotary evaporation, precipitate the catalyst with n-hexane, filter, perform rotary evaporation, and dry in vacuo to obtain modified cis-1,4-polybutadiene; the mass ratio of cis-1,4-polybutadiene to the alkenyl compound is 10:1; the alkenyl compound is a mixture of norbornenyl quaternary ammonium salt, cyclooctene, and maleamide disiloxane with a mass ratio of 1:5:3; the ratio of cis-1,4-polybutadiene to tetrahydrofuran is 8 g / 100 mL; mix the modified cis-1,4-polybutadiene and p-toluenesulfonyl hydrazide, add o-xylene to dissolve them in a nitrogen atmosphere, add tri-n-propylamine, and react at 133 °C for 225 min; perform rotary evaporation, precipitate with ethanol, filter, wash, and dry to obtain hydrogenated cis-1,4-polybutadiene; the mass ratio of modified cis-1,4-polybutadiene, p-toluenesulfonyl hydrazide, and tri-n-propylamine is 10:2:0.6; the ratio of modified cis-1,4-polybutadiene to o-xylene is 10 g / 100 mL;

[0088] Step 2: Place the hydrogenated cis-1,4-polybutadiene in a mixer and plasticate for 2 min; add the filler in three portions at intervals of 1 min each, then perform mixing at 50 °C for 12 min at a rotational speed of 40 rpm and a pressure of 0.5 MPa; then transfer it to an open mill, thin-pass at 40 °C for 5 times, take off the sheet and cool, and pelletize to obtain the filler / hydrogenated cis-1,4-polybutadiene mixture;

[0089] Premix high-density polyethylene, low-density polyethylene, and linear low-density polyethylene at 80 °C for 8 min; add a compatibilizer, raise the temperature to 100 °C, and mix for 12 min; lower the temperature to 75 °C, add an antioxidant and a light stabilizer, mix for 7 min, add Stat-Rite C-2300, and continue mixing for 6 min; add the filler / hydrogenated cis-1,4-polybutadiene mixture and Armostat 600, and continue mixing at 60 °C for 6 min; finally add a lubricant and mix for 4 min to obtain a premix;

[0090] Extrude, and the extrusion process conditions are as follows: in a twin-screw extruder, extrude and plasticate, and form polyethylene pellets by air-cooled strand pelletizing. The temperatures of each zone of the extruder are as follows: zone 1 is 170 °C, zone 2 is 190 °C, zone 3 is 200 °C, zone 4 is 190 °C, the die head temperature is 180 °C, and the rotational speed is 300 rpm to obtain a polyethylene material; the polyethylene material includes the following components: 78 parts of high-density polyethylene, 15 parts of low-density polyethylene, 5 parts of linear low-density polyethylene, 8 parts of hydrogenated cis-1,4-polybutadiene, 10 parts of filler, and 3.4 parts of additives; the additives include 1 part of antistatic agent, 1 part of compatibilizer, 0.3 part of antioxidant, 0.6 part of light stabilizer, and 0.5 part of lubricant.

[0091] Example 2: A preparation method of a wear-resistant and antistatic polyethylene material, including the following process:

[0092] Step 1: Mix norbornene dianhydride and 3-dimethylaminopropylamine in toluene and reflux for 24 h to obtain dimethylaminopropyl norbornene; mix dimethylaminopropyl norbornene and lithium aluminum hydride in anhydrous ether and dichloromethane, stir and react for 24 h; add methyl iodide and stir for 12 h; filter, distill under reduced pressure, wash, and dry to obtain norbornenyl quaternary ammonium salt; the molar ratio of norbornene dianhydride, 3-dimethylaminopropylamine, lithium aluminum hydride, and methyl iodide is 1:1.3:0.27:2.1; the ratio of norbornene dianhydride to toluene is 10 g:4 mL; the ratio of dimethylaminopropyl norbornene, anhydrous ether, and dichloromethane is 10 g:30 mL:70 mL;

[0093] Mix amino silicone oil, 2 mol% triethylamine catalyst, and anhydrous toluene, and slowly add maleic anhydride under the protection of nitrogen atmosphere, finish adding within 30 min, heat to 35 °C, and react for 4 h; raise the temperature to 90 °C and continue to react for 3.5 h; cool to 60 °C, add 5% sodium bicarbonate to wash, separate the liquid, take the organic layer to dry, distill under reduced pressure, chromatograph, and vacuum dry to obtain maleamide-based disiloxane; the molar ratio of amino silicone oil to maleic anhydride is 2.3:1; the ratio of amino silicone oil to anhydrous toluene is 10 g:4 mL, and the amino silicone oil is N-phenyl-3-aminopropyltrimethoxysilane;

[0094] Dry and mix cis-1,4-polybutadiene rubber and vinyl compound, dissolve in tetrahydrofuran under the protection of nitrogen atmosphere, add 0.15 wt% Grubbs II generation catalyst, and react at 42 °C for 45 min; end the reaction with anhydrous methanol, rotary evaporate, precipitate the catalyst with n-hexane, filter, rotary evaporate, and vacuum dry to obtain modified cis-1,4-polybutadiene rubber; the mass ratio of cis-1,4-polybutadiene rubber to vinyl compound is 10:1.5; mix norbornenyl quaternary ammonium salt, cyclooctene, and maleamide-based disiloxane with a mass ratio of 3:8:5; the ratio of cis-1,4-polybutadiene rubber to tetrahydrofuran is 5.5 g / 100 mL;

[0095] Mix modified cis-1,4-polybutadiene rubber and p-toluenesulfonyl hydrazide, add o-xylene to dissolve in nitrogen atmosphere, add tri-n-propylamine, and react at 135 °C for 237 min; rotary evaporate, precipitate with ethanol, filter, wash, and dry to obtain hydrogenated cis-1,4-polybutadiene rubber; the mass ratio of modified cis-1,4-polybutadiene rubber, p-toluenesulfonyl hydrazide, and tri-n-propylamine is 10:2.5:1.0; the ratio of modified cis-1,4-polybutadiene rubber to o-xylene is 10 g / 100 mL;

[0096] Step 2: Place the hydrogenated cis-1,4-polybutadiene rubber in a mixer and plasticate for 2.5 min; add the filler in three portions at intervals of 1 min, then knead at 60 °C for 9 min, with a rotational speed of 50 rpm and a pressure of 0.6 MPa; then transfer to an open mill, thin pass 4 times at 45 °C, take off the sheet and cool, cut into pellets to obtain the filler / hydrogenated cis-1,4-polybutadiene rubber mixture;

[0097] Pre-mix high-density polyethylene, low-density polyethylene, and linear low-density polyethylene at 90 °C for 6 min; add a compatibilizer, raise the temperature to 110 °C, and mix for 10 min; lower the temperature to 78 °C, add an antioxidant and a light stabilizer, mix for 6 min, add Stat-Rite C-2300, and continue mixing for 5 min; add a filler / hydrogenated butadiene rubber mixture and Armostat 600, and continue mixing at 70 °C for 5 min; finally, add a lubricant and mix for 3 min to obtain a premix.

[0098] Extrude. The extrusion process conditions are as follows: In a twin-screw extruder, extrude and plasticize, and form polyethylene pellets by air-cooled strand cutting. The temperatures of each zone of the extruder are successively: zone 1 at 170 °C, zone 2 at 190 °C, zone 3 at 200 °C, zone 4 at 190 °C, and the die head temperature at 180 °C, with a rotational speed of 300 rpm to obtain a polyethylene material; The polyethylene material includes the following components: 82 parts of high-density polyethylene, 12 parts of low-density polyethylene, 4 parts of linear low-density polyethylene, 11 parts of hydrogenated butadiene rubber, 15 parts of filler, and 5.4 parts of additives; The additives include 2 parts of antistatic agent, 2 parts of compatibilizer, 0.3 part of antioxidant, 0.6 part of light stabilizer, and 0.5 part of lubricant.

[0099] Example 3: A preparation method of a wear-resistant and antistatic polyethylene material, including the following processes:

[0100] Step 1: Mix maleic anhydride and 3-dimethylaminopropylamine in toluene and reflux for 24 h to obtain dimethylaminopropylnorbornene; Mix dimethylaminopropylnorbornene and lithium aluminum hydride in anhydrous ether and dichloromethane, stir and react for 24 h; Add methyl iodide and stir for 12 h; Filter, distill under reduced pressure, wash, and dry to obtain norbornenyl quaternary ammonium salt; The molar ratio of maleic anhydride, 3-dimethylaminopropylamine, lithium aluminum hydride, and methyl iodide is 1:1.5:0.30:2.2; The ratio of maleic anhydride to toluene is 10 g:5 mL; The ratio of dimethylaminopropylnorbornene, anhydrous ether, and dichloromethane is 10 g:40 mL:60 mL;

[0101] Mix aminopolysiloxane, 3 mol% triethylamine catalyst, and anhydrous toluene, and slowly add maleic anhydride under nitrogen atmosphere protection, finishing the addition within 30 min, heat to 50 °C, and react for 2 h; Raise the temperature to 93 °C and continue reacting for 3 h; Cool to 60 °C, add 5% sodium bicarbonate for washing, separate the liquid, take the organic layer for drying, distill under reduced pressure, chromatograph, and vacuum dry to obtain maleamide disiloxane; The molar ratio of aminopolysiloxane to maleic anhydride is 2.5:1; The ratio of aminopolysiloxane to anhydrous toluene is 10 g:5 mL; The aminopolysiloxane is 3-aminopropyltriethoxysilane;

[0102] Dry the cis-1,4-polybutadiene and the alkenyl compound, mix them, dissolve them in tetrahydrofuran under the protection of a nitrogen atmosphere, add 0.30 wt% of the Grubbs II-generation catalyst, and react at 45 °C for 60 min; terminate the reaction with anhydrous methanol, perform rotary evaporation, precipitate the catalyst with n-hexane, filter, perform rotary evaporation, and dry under vacuum to obtain modified cis-1,4-polybutadiene; the mass ratio of cis-1,4-polybutadiene to the alkenyl compound is 10:2; mix norbornenyl quaternary ammonium salt, cyclooctene, and maleamide disiloxane with a mass ratio of 5:12:8; the ratio of cis-1,4-polybutadiene to tetrahydrofuran is 5 g / 100 mL; mix the modified cis-1,4-polybutadiene and p-toluenesulfonyl hydrazide, add o-xylene to dissolve them in a nitrogen atmosphere, add tri-n-propylamine, and react at 137 °C for 250 min; perform rotary evaporation, precipitate with ethanol, filter, wash, and dry to obtain hydrogenated cis-1,4-polybutadiene; the mass ratio of modified cis-1,4-polybutadiene, p-toluenesulfonyl hydrazide, and tri-n-propylamine is 10:3:1.5; the ratio of modified cis-1,4-polybutadiene to o-xylene is 10 g / 100 mL;

[0103] Step 2: Place the hydrogenated cis-1,4-polybutadiene in a mixer and plasticize it for 3 min; add the filler in three portions at intervals of 1 min each, then perform mixing at 70 °C for 6 min at a rotational speed of 60 rpm and a pressure of 0.8 MPa; then transfer it to an open mill, perform thin pass at 50 °C three times, take off the sheet and cool it, and cut into pellets to obtain a filler / hydrogenated cis-1,4-polybutadiene mixture;

[0104] Premix high-density polyethylene, low-density polyethylene, and linear low-density polyethylene at 100 °C for 5 min; add a compatibilizer, raise the temperature to 120 °C, and mix for 8 min; lower the temperature to 80 °C, add an antioxidant and a light stabilizer, mix for 5 min, add Stat-Rite C-2300, and continue mixing for 4 min; add the filler / hydrogenated cis-1,4-polybutadiene mixture and Armostat 600, and continue mixing at 80 °C for 4 min; finally add a lubricant and mix for 2 min to obtain a premix;

[0105] Extrude, and the extrusion process conditions are as follows: in a twin-screw extruder, extrude and plasticize, and form polyethylene pellets by air-cooled strand cutting. The temperatures of each zone of the extruder are as follows: zone 1 is 170 °C, zone 2 is 190 °C, zone 3 is 200 °C, zone 4 is 190 °C, the die head temperature is 180 °C, and the rotational speed is 300 rpm to obtain a polyethylene material; the polyethylene material includes the following components: 85 parts of high-density polyethylene, 10 parts of low-density polyethylene, 3 parts of linear low-density polyethylene, 15 parts of hydrogenated cis-1,4-polybutadiene, 20 parts of filler, and 7.4 parts of additives; the additives include 3 parts of antistatic agent, 3 parts of compatibilizer, 0.3 part of antioxidant, 0.6 part of light stabilizer, and 0.5 part of lubricant.

[0106] Comparative Example 1: A preparation method of a wear-resistant and antistatic polyethylene material, including the following process:

[0107] Step 1: Mix norbornene dianhydride and isohexylamine in toluene and reflux for 24 h to obtain amino norbornene; mix amino norbornene and lithium aluminum hydride in anhydrous ether and dichloromethane and stir for 24 h; add methyl iodide and stir for 12 h; filter, distill under reduced pressure, wash, and dry to obtain norbornenyl quaternary ammonium salt; the molar ratio of norbornene dianhydride, 3-isohexylamine, lithium aluminum hydride, and methyl iodide is 1:1.2:0.12:1.0; the ratio of norbornene dianhydride to toluene is 10 g:3 mL; the ratio of amino norbornene, anhydrous ether, and dichloromethane is 10 g:20 mL:80 mL;

[0108] The subsequent process steps are the same as those in Example 1 to obtain a polyethylene material.

[0109] Comparative Example 2: A method for preparing a wear-resistant and antistatic polyethylene material, including the following process:

[0110] Step 1: The olefinic compound is a mixture of cyclooctene and maleamide disiloxane with a mass ratio of 5:3;

[0111] The other process steps are the same as those in Example 1 to obtain a polyethylene material.

[0112] Comparative Example 3: A method for preparing a wear-resistant and antistatic polyethylene material, including the following process:

[0113] Step 1: The olefinic compound is a mixture of norbornene, cyclooctene, and maleic acid with a mass ratio of 1:5:1;

[0114] The other process steps are the same as those in Example 1 to obtain a polyethylene material.

[0115] Comparative Example 4: A method for preparing a wear-resistant and antistatic polyethylene material, including the following process:

[0116] Premix high-density polyethylene, low-density polyethylene, and linear low-density polyethylene at 80 °C for 8 min; add a compatibilizer and a filler, raise the temperature to 100 °C, and mix for 12 min; lower the temperature to 75 °C, add an antioxidant and a light stabilizer, mix for 7 min, add Stat-Rite C-2300, and continue to mix for 6 min; add cis-1,4-polybutadiene rubber and Armostat 600, and continue to mix at 60 °C for 6 min; finally add a lubricant and mix for 4 min to obtain a premix;

[0117] The extrusion process steps are the same as those in Example 1 to obtain a polyethylene material.

[0118] Experiment: The polyethylene materials obtained in Examples 1-3 and Comparative Examples 1-4 were blow molded in an extrusion hollow blow molding machine. The temperatures of each zone were as follows: Zone 1: 165°C, Zone 2: 185°C, Zone 3: 195°C, the head: 195°C, and the rotation speed: 50 rpm; the blowing pressure was 0.6 MPa, the blowing time was 5 seconds, the mold temperature was 35°C, and the cooling time was 25 s to obtain specimens. The properties of the specimens were tested respectively and the test results were recorded:

[0119] Mechanical property test: Referring to GB / T 1040.2 as the reference standard, the tensile properties of the experiment were tested using a universal testing machine at a tensile rate of 50 mm / min and an experimental temperature of 23 ± 2°C;

[0120] Antistatic property test: Referring to GB / T 1410 as the reference standard, the surface resistivity of the specimens was tested using a high resistance meter with an electrode spacing of 20 mm, an experimental environment of 23 ± 2°C, and 50% RH;

[0121] Wear resistance test: The wear resistance of the specimens was tested using a DIN abrasion testing machine with a load of 1 kg and a wear path of 40 m;

[0122] Impact property test: Referring to GB / T 1043 as the reference standard, the impact strength (notch) of the specimens was tested using a pendulum impact testing machine.

[0123]

[0124]

[0125] According to the data in the above table, the following conclusions can be clearly obtained:

[0126] The polyethylene materials obtained in Examples 1-3 were compared with the polyethylene materials obtained in Comparative Examples 1-4. From the test results,

[0127] Compared with the comparative examples, the polyethylene materials obtained in Examples 1-3 had higher tensile strength, elongation at break, notch impact strength data and lower surface resistivity and DIN wear amount. This fully demonstrated that the present invention achieved the improvement of the wear resistance and antistatic properties of the prepared polyethylene materials, and at the same time improved their mechanical properties.

[0128] Compared with Example 1, the selection of raw materials for preparing norbornenyl quaternary ammonium salt in Comparative Example 1 is different; in Comparative Example 2, the alkenyl compound is cyclooctene and maleamide disiloxane; in Comparative Example 3, the alkenyl compound is norbornene, cyclooctene and maleic acid; the cis-butadiene rubber in Comparative Example 4 is not modified. For the polyethylene materials obtained in Comparative Examples 1-4, the data of tensile strength, elongation at break and notched impact strength decrease, while the surface resistivity and DIN abrasion increase. It can be seen that the composition and process settings of the polyethylene material in the present invention can promote the comprehensive improvement of its wear resistance, antistatic performance and mechanical properties.

[0129] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

Claims

1. A preparation method of a wear-resistant and antistatic polyethylene material, characterized in that: It includes the following processes: Mix high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cis-1,4-polybutadiene rubber, filler and additives, and extrude to obtain a polyethylene material.

2. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 1, characterized in that: The cis-1,4-polybutadiene rubber is subjected to a modification treatment, and the specific process is as follows: Mix cis-1,4-polybutadiene rubber and an alkenyl compound, dissolve in tetrahydrofuran under the protection of a nitrogen atmosphere, add a catalyst, and react at a temperature of 40-45 °C for 30-60 min to obtain a modified cis-1,4-polybutadiene rubber; Hydrogenate to obtain hydrogenated cis-1,4-polybutadiene rubber; The alkenyl compound is a mixture of a norbornenyl quaternary ammonium salt, cyclooctene, and maleamide disiloxane.

3. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 2, characterized in that: The norbornenyl quaternary ammonium salt is prepared by the following process: Mix norbornene dianhydride and 3-dimethylaminopropylamine in toluene and reflux for 24 h to obtain dimethylpropylaminonorbornene; Mix dimethylpropylaminonorbornene and lithium aluminum hydride in anhydrous ether and dichloromethane, stir and react for 24 h; add methyl iodide and stir for 12 h to obtain a norbornenyl quaternary ammonium salt.

4. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 3, characterized in that: The maleamide disiloxane is prepared by the following process: Mix an amino siloxane, a catalyst, and anhydrous toluene, slowly add maleic anhydride under the protection of a nitrogen atmosphere, add it within 30 min, heat to 25-50 °C, and react for 2-6 h; raise the temperature to 85-93 °C and continue to react for 3-4 h to obtain maleamide disiloxane.

5. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 2, characterized in that: The mass ratio of the norbornenyl quaternary ammonium salt, cyclooctene, and maleamide disiloxane is (0.1-0.5):(0.5-1.2):(0.3-0.8).

6. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 2, wherein: The hydrogenation process is as follows: Mix the modified cis-1,4-polybutadiene rubber and p-toluenesulfonylhydrazide, dissolve in o-xylene under a nitrogen atmosphere, add tri-n-propylamine, and react at a temperature of 133-137 °C for 225-250 min to obtain hydrogenated cis-1,4-polybutadiene rubber.

7. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 6, characterized in that: The mass ratio of the modified cis-1,4-polybutadiene rubber, p-toluenesulfonylhydrazide, and tri-n-propylamine is 10:(2-3):(0.6-1.5).

8. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 1, wherein: The polyethylene material includes the following components: 70-85 parts of high-density polyethylene, 10-15 parts of low-density polyethylene, 3-5 parts of linear low-density polyethylene, 8-15 parts of cis-1,4-polybutadiene rubber, 10-20 parts of filler, and 2-9 parts of additives.

9. The preparation method of a wear-resistant and antistatic polyethylene material according to claim 8, wherein: The additives include 0.1-5 parts of an antistatic agent, 1-3 parts of a compatibilizer, 0.1-0.3 parts of an antioxidant, 0.2-0.6 parts of a light stabilizer, and 0.2-1.0 parts of a lubricant.

10. A wear-resistant and antistatic polyethylene material prepared by the preparation method according to any one of claims 1-9.

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