A polyolefin plastic pipe and its preparation method

Abstract

The present invention discloses a polyolefin plastic pipe and a preparation method thereof. By using a modified additive, conductive particles and LLDPE, under the action of dicumyl peroxide, the modified additive and the conductive particles are grafted with LLDPE molecular chains, and then extruded and shaped. The main chain of the modified additive is an organosilicon long chain, which can increase the high-temperature resistance of the material after grafting with LLDPE. At the same time, the polypyrrole long chain on the side chain and the conductive particles cooperate to make the pipe conductive. After the conductive particles are linked with the LLDPE molecular chains, a core-shell structure with LLDPE as the shell and conductive particles as the core is formed. At the same time, there is a cage-shaped cavity between the core and the shell, which greatly improves the mechanical properties of the pipe. And the surface treatment of carbon black effectively avoids the problem of poor compatibility of the conductive particles.

Description

Technical Field

[0001] The invention relates to the technical field of pipe preparation, and in particular to a polyolefin plastic pipe and a preparation method thereof. Background Art

[0002] The urban integrated pipe gallery system has an important application basis in the urban core area, central business district, underground high-intensity concentrated development area, important squares, and main road areas. The underground integrated pipe gallery integrates urban pipelines such as water supply, rainwater, sewage, recycled water, natural gas, heat, electricity, and communications. It can effectively and intensively utilize underground space, coordinate various pipelines, and reduce the impact on the daily operation of the city. Different medium pipes in the pipe gallery have different requirements. Traditional power pipes have good insulation properties, which makes it easy to generate static electricity when rubbed. The generation of static electricity makes it impossible to use the power pipe normally under special circumstances. There are two ways to avoid static electricity. One method is to introduce static electricity into the raw materials so that it can move to the surface and make its hydrophilic branches produce antistatic effects, that is, reduce the surface resistance. The other is to mix fillers with good conductivity, but filler agglomeration problems will occur during the preparation process. Summary of the invention

[0003] The purpose of the present invention is to provide a polyolefin plastic pipe and a preparation method thereof, which solves the problem that the current polyolefin plastic pipe has poor toughness and cannot conduct electricity.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] A method for preparing a polyolefin plastic pipe comprises the following steps:

[0006] The modified additive, conductive particles, dicumyl peroxide and LLDPE are mixed and added into a twin-screw extruder, and extruded and shaped at temperatures of 120° C., 130° C., 150° C., 180° C. and 160° C., and cooled to form a polyolefin plastic pipe.

[0007] Furthermore, the mass ratio of the modified additive, the conductive particles, dicumyl peroxide and LLDPE is 10-13:20-25:0.2-0.5:100.

[0008] Further, the modified additive is prepared by the following steps:

[0009] Step A1: Disperse Y-aminopropylmethyldiethoxysilane in toluene, add p-toluenesulfonic acid, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 112 - 115 °C, stir and add maleic anhydride, and react for 4 - 6 h to obtain Intermediate 1. Add Intermediate 1 to deionized water, under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 25 - 30 °C, stir for 3 - 5 min, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 55 - 65 °C, keep warm for 5 - 10 min, add D4 and 1,1,3,3-tetramethyldisiloxane, and react for 3 - 5 h to obtain polysiloxane;

[0010] Step A2: Mix the polysiloxane and a benzene solution of acrylic acid, under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 50 - 60 °C, stir and add chloroplatinic acid, after adding, raise the temperature to 60 - 65 °C, and react for 3 - 4 h to obtain Intermediate 2. Mix Intermediate 2, oxalyl chloride, dichloromethane, and N,N-dimethylformamide, under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 20 - 25 °C, react for 1 - 2 h, then add ammonia water, and continue to react for 30 - 40 min to obtain amide-capped polysiloxane;

[0011] Step A3: Mix the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran, and glacial acetic acid evenly, under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 100 - 105 °C, react for 4 - 6 h to obtain modified polysiloxane. Dissolve the modified polysiloxane in toluene, under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 20 - 25 °C, stir and add ferric chloride hexahydrate and pyrrole, and react for 20 - 25 h to obtain a modified additive.

[0012] Furthermore, the dosage ratio of Y-aminopropylmethyldiethoxysilane, p-toluenesulfonic acid, and maleic anhydride described in Step A1 is 1 mL:1.3 mL:7.1 g, and the dosage ratio of Intermediate 1, deionized water, D4, and 1,1,3,3-tetramethyldisiloxane is 10 mmol:2 mL:1 mmol:8 mmol, and the dosage of concentrated sulfuric acid is 3 - 5% of the sum of the masses of Intermediate 1, D4, and 1,1,3,3-tetramethyldisiloxane.

[0013] Furthermore, the molar ratio of the polysiloxane and acrylic acid described in Step A2 is 1:2, the dosage of chloroplatinic acid is 0.01 - 0.03‰ of the mass of acrylic acid, and the dosage ratio of Intermediate 2, oxalyl chloride, dichloromethane, N,N-dimethylformamide, and ammonia water is 40 mmol:60 mL:140 mmol:0.15 mL:45 mL.

[0014] Further, the dosage ratio of the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran, and glacial acetic acid described in step A3 is 3 mmol: 3 mmol: 4 mL, and the molar ratio of the modified polysiloxane, ferric chloride hexahydrate, and pyrrole is 3: 4: 10.

[0015] Further, the conductive particles are prepared by the following steps:

[0016] Step B1: Put carbon black into a high-temperature atmosphere furnace, introduce nitrogen, heat it up to 1000 °C at a heating rate of 5 °C / min, introduce carbon dioxide, keep it warm for 2 - 3 h, after cooling to room temperature, disperse it in ethanol, add acetic acid and KH550, and under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 20 - 25 °C, stir for 30 - 40 min, heat up to 80 - 85 °C, and continue to stir for 3 - 5 h to obtain pretreated carbon black;

[0017] Step B2: Disperse the pretreated carbon black in ethanol, add ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate, and under the conditions of a frequency of 20 - 30 kHz, a temperature of 20 - 25 °C, and an alkaline condition, perform ultrasonic treatment for 1 - 1.5 h, heat up to 80 - 85 °C, distill off ethanol, and calcine the substrate at 900 - 950 °C under nitrogen protection for 2 - 3 h to obtain modified carbon black;

[0018] Step B3: Disperse the modified carbon black in tetrahydrofuran, add KH560, and under the conditions of a rotation speed of 150 - 200 r / min, a temperature of 20 - 25 °C, and an alkaline condition, react for 3 - 5 h, then add KH550, heat up to 60 - 70 °C, and react for 10 - 15 h, cool to room temperature, add ammonium fluoride, and continue to stir for 20 - 25 h, filter to remove the filtrate to obtain a modified matrix;

[0019] Step B4: Disperse the modified matrix in toluene, add p-toluenesulfonic acid, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 112 - 115 °C, stir and add maleic anhydride, react for 2 - 3 h, filter to remove the filtrate to obtain conductive particles.

[0020] Further, the dosage ratio of the carbon black, acetic acid, and KH550 described in step B1 is 1 g: 1 mL: 6.5 mg.

[0021] Further, the dosage ratio of the pretreated carbon black, ferric nitrate nonahydrate, and sodium dodecylbenzenesulfonate in step B2 is 1 g: 185 mg: 40 mg.

[0022] Further, the dosage ratio of the modified matrix, KH560, KH550, and ammonium fluoride in step B3 is 1 g: 1.1 mL: 3 mL: 0.3 g.

[0023] Further, the dosage ratio of amino group, maleic anhydride and p-toluenesulfonic acid on the modified matrix described in step B4 is 1 mol: 1.3 mol: 6.4 g.

[0024] Advantages of the present invention: A polyolefin plastic pipe prepared by the present invention is obtained by grafting a modified additive, conductive particles and LLDPE under the action of diisopropylbenzene peroxide, so that the modified additive and conductive particles are grafted to the LLDPE molecular chain and then extruded and shaped. The modified additive reacts with maleic anhydride under the action of p-toluenesulfonic acid using Y-aminopropylmethyldiethoxysilane as a raw material to form a maleimide structure, and intermediate 1 is prepared. Intermediate 1 is hydrolyzed and then polymerized with D4 and 1,1,3,3-tetramethyldihydroxydisiloxane to form a dihydroxy-terminated polysiloxane. Under the action of chloroplatinic acid, the Si-H on the polysiloxane reacts with the double bond on acrylic acid to prepare intermediate 2. Intermediate 2 is treated with oxalyl chloride to convert the carboxyl group on intermediate 2 into an acyl chloride, and then reacts with ammonia water to form an amide structure, and an amide-terminated polysiloxane is prepared. Using the amide-terminated polysiloxane and 2,5-dimethoxytetrahydrofuran as raw materials, pyrrole is formed by the Clauson-Kaas synthesis method, and then ferric chloride hexahydrate and pyrrole are added to form a polypyrrole side chain to prepare a modified additive. The conductive particles are first oxidized using carbon black as a raw material, and then surface-treated with KH550 to graft amino groups on the surface to prepare pretreated carbon black. Then, nano-metal iron is loaded on the surface of the pretreated carbon black using ferric nitrate nonahydrate to prepare modified carbon black. The modified carbon black is treated with KH560. Under alkaline conditions, the amino group on the modified carbon black reacts with the epoxy group on KH560, and then KH550 is added, and a condensation reaction occurs under the action of ammonium fluoride to form a cage-like polyhedral oligomeric silsesquioxane. Then, maleic anhydride is added to react with the amino group on the cage-like polyhedral oligomeric silsesquioxane to form a maleimide structure. The main chain of the modified additive is an organosilicon long chain, which can increase the high-temperature resistance of the material after grafting with LLDPE. At the same time, the polypyrrole long chain on the side chain and the conductive particles cooperate to make the pipe conductive. After the conductive particles are linked to the LLDPE molecular chain, a core-shell structure with LLDPE as the shell and conductive particles as the core is formed. At the same time, there is a cage-like cavity between the core and the shell, which greatly improves the mechanical properties of the pipe. And the surface treatment of carbon black effectively avoids the problem of poor compatibility of conductive particles. Detailed implementation manners

[0025] 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 the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0026] Example 1

[0027] A preparation method of a polyolefin plastic pipe specifically includes the following steps:

[0028] Mix the modified additive, conductive particles, dicumyl peroxide, and LLDPE, add them to a twin-screw extruder, and under the conditions of temperatures of 120°C, 130°C, 150°C, 180°C, and 160°C in sequence, extrude and shape and cool to obtain the polyolefin plastic pipe.

[0029] The mass ratio of the modified additive, conductive particles, dicumyl peroxide, and LLDPE is 10:20:0.2:100, and the model of LLDPE is 7042.

[0030] The modified additive is prepared by the following steps:

[0031] Step A1: Disperse Y-aminopropylmethyldiethoxysilane in toluene, add p-toluenesulfonic acid, under the conditions of a rotation speed of 150 r / min and a temperature of 112°C, stir and add maleic anhydride, and react for 4 h to obtain intermediate 1. Add intermediate 1 to deionized water, under the conditions of a rotation speed of 200 r / min and a temperature of 25°C, stir for 3 min, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 55°C, keep warm for 5 min, add D4 and 1,1,3,3-tetramethyldisiloxane, and react for 3 h to obtain polysiloxane;

[0032] Step A2: Mix the polysiloxane and a benzene solution of acrylic acid, under the conditions of a rotation speed of 200 r / min and a temperature of 50°C, stir and add chloroplatinic acid, after adding, raise the temperature to 60°C, and react for 3 h to obtain intermediate 2. Mix intermediate 2, oxalyl chloride, dichloromethane, and N,N-dimethylformamide, under the conditions of a rotation speed of 150 r / min and a temperature of 20°C, react for 1 h, then add ammonia water and continue to react for 30 min to obtain amide-terminated polysiloxane;

[0033] Step A3: Mix the amide-terminated modified polysiloxane, 2,5-dimethoxytetrahydrofuran, and glacial acetic acid evenly, under the conditions of a rotation speed of 150 r / min and a temperature of 100°C, react for 4 h to obtain modified polysiloxane. Dissolve the modified polysiloxane in toluene, under the conditions of a rotation speed of 200 r / min and a temperature of 20°C, stir and add ferric chloride hexahydrate and pyrrole, and react for 20 h to obtain the modified additive.

[0034] The dosage ratio of Y-aminopropylmethyldiethoxysilane, p-toluenesulfonic acid and maleic anhydride described in Step A1 is 1 mL: 1.3 mL: 7.1 g, and the dosage ratio of Intermediate 1, deionized water, D4 and 1,1,3,3-tetramethyldisiloxane is 10 mmol: 2 mL: 1 mmol: 8 mmol. The dosage of concentrated sulfuric acid is 3% of the sum of the masses of Intermediate 1, D4 and 1,1,3,3-tetramethyldisiloxane.

[0035] The molar ratio of polysiloxane and acrylic acid described in Step A2 is 1:2, and the dosage of chloroplatinic acid is 0.01‰ of the mass of acrylic acid. The dosage ratio of Intermediate 2, oxalyl chloride, dichloromethane, N,N-dimethylformamide and ammonia water is 40 mmol: 60 mL: 140 mmol: 0.15 mL: 45 mL.

[0036] The dosage ratio of amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran and glacial acetic acid described in Step A3 is 3 mmol: 3 mmol: 4 mL, and the molar ratio of modified polysiloxane, ferric chloride hexahydrate and pyrrole is 3:4:10.

[0037] The described conductive particles are prepared by the following steps:

[0038] Step B1: Put carbon black into a high-temperature atmosphere furnace, introduce nitrogen, heat it up to 1000 °C at a heating rate of 5 °C / min, introduce carbon dioxide, keep it warm for 2 h, cool it to room temperature, disperse it in ethanol, add acetic acid and KH550, and stir for 30 min at a rotation speed of 200 r / min and a temperature of 20 °C. Then heat it up to 80 °C and continue stirring for 3 h to obtain pretreated carbon black.

[0039] Step B2: Disperse the pretreated carbon black in ethanol, add ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate, and ultrasonically treat it for 1 h under the conditions of a frequency of 20 kHz, a temperature of 20 °C and an alkaline condition. Then heat it up to 80 °C and distill off ethanol. Roast the substrate at 900 °C under nitrogen protection for 2 h to obtain modified carbon black.

[0040] Step B3: Disperse the modified carbon black in tetrahydrofuran, add KH560, and react for 3 h at a rotation speed of 150 r / min, a temperature of 20 °C and an alkaline condition. Then add KH550, heat it up to 60 °C and react for 10 h. Cool it to room temperature, add ammonium fluoride, and continue stirring for 20 h. Filter off the filtrate to obtain a modified matrix.

[0041] Step B4: Disperse the modified matrix in toluene, add p-toluenesulfonic acid, stir and add maleic anhydride at a rotation speed of 150 r / min and a temperature of 112 °C, and react for 2 h. Filter off the filtrate to obtain conductive particles.

[0042] The dosage ratio of carbon black, acetic acid and KH550 described in step B1 is 1 g: 1 mL: 6.5 mg.

[0043] The dosage ratio of the pretreated carbon black, ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate described in step B2 is 1 g: 185 mg: 40 mg.

[0044] The dosage ratio of KH560, KH550 and ammonium fluoride on the modified matrix described in step B3 is 1 g: 1.1 mL: 3 mL: 0.3 g.

[0045] The dosage ratio of amino group, maleic anhydride and p-toluenesulfonic acid on the modified matrix described in step B4 is 1 mol: 1.3 mol: 6.4 g.

[0046] Example 2

[0047] A preparation method of a polyolefin plastic pipe specifically includes the following steps:

[0048] Mix the modified additive, conductive particles, dicumyl peroxide and LLDPE, add them into a twin-screw extruder, and under the conditions of temperatures of 120 °C, 130 °C, 150 °C, 180 °C and 160 °C in sequence, extrude and shape and cool to obtain the polyolefin plastic pipe.

[0049] The mass ratio of the modified additive, conductive particles, dicumyl peroxide and LLDPE is 12: 23: 0.4: 100, and the model of LLDPE is 7042.

[0050] The modified additive is prepared by the following steps:

[0051] Step A1: Disperse Y-aminopropylmethyldiethoxysilane in toluene, add p-toluenesulfonic acid, under the conditions of a rotation speed of 150 r / min and a temperature of 115 °C, stir and add maleic anhydride, react for 5 h to obtain intermediate 1, add intermediate 1 into deionized water, under the conditions of a rotation speed of 200 r / min and a temperature of 30 °C, stir for 4 min, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 60 °C, keep the temperature for 8 min, add D4 and 1,1,3,3-tetramethyldisiloxane, and react for 4 h to obtain polysiloxane;

[0052] Step A2: Mix the benzene solutions of polysiloxane and acrylic acid, stir and add chloroplatinic acid under the conditions of a rotation speed of 200 r / min and a temperature of 55 °C. After the addition is completed, raise the temperature to 63 °C and react for 3.5 h to obtain Intermediate 2. Mix Intermediate 2, oxalyl chloride, dichloromethane and N,N-dimethylformamide, and react for 1.5 h under the conditions of a rotation speed of 150 r / min and a temperature of 25 °C. Then add ammonia water and continue to react for 35 min to obtain amide-capped polysiloxane;

[0053] Step A3: Mix the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran and glacial acetic acid evenly, and react for 5 h under the conditions of a rotation speed of 150 r / min and a temperature of 105 °C to obtain modified polysiloxane. Dissolve the modified polysiloxane in toluene, stir and add ferric chloride hexahydrate and pyrrole under the conditions of a rotation speed of 200 r / min and a temperature of 25 °C, and react for 20 h to obtain a modified additive.

[0054] The dosage ratio of Y-aminopropylmethyldiethoxysilane, p-toluenesulfonic acid and maleic anhydride described in Step A1 is 1 mL: 1.3 mL: 7.1 g. The dosage ratio of Intermediate 1, deionized water, D4 and 1,1,3,3-tetramethyldisiloxane is 10 mmol: 2 mL: 1 mmol: 8 mmol. The dosage of concentrated sulfuric acid is 4% of the sum of the masses of Intermediate 1, D4 and 1,1,3,3-tetramethyldisiloxane.

[0055] The molar ratio of polysiloxane and acrylic acid described in Step A2 is 1:2. The dosage of chloroplatinic acid is 0.02‰ of the mass of acrylic acid. The dosage ratio of Intermediate 2, oxalyl chloride, dichloromethane, N,N-dimethylformamide and ammonia water is 40 mmol: 60 mL: 140 mmol: 0.15 mL: 45 mL.

[0056] The dosage ratio of the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran and glacial acetic acid described in Step A3 is 3 mmol: 3 mmol: 4 mL. The molar ratio of the modified polysiloxane, ferric chloride hexahydrate and pyrrole is 3:4:10.

[0057] The conductive particles are prepared by the following steps:

[0058] Step B1: Put carbon black into a high-temperature atmosphere furnace, introduce nitrogen, and raise the temperature to 1000 °C at a heating rate of 5 °C / min. Then introduce carbon dioxide, keep the temperature for 2 h, cool to room temperature, disperse it in ethanol, add acetic acid and KH550, and stir for 35 min under the conditions of a rotation speed of 300 r / min and a temperature of 20 °C. Then raise the temperature to 85 °C and continue to stir for 4 h to obtain pretreated carbon black;

[0059] Step B2: Disperse the pretreated carbon black in ethanol, add ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate, and under the conditions of a frequency of 25 kHz, a temperature of 25 °C, and an alkaline condition, perform ultrasonic treatment for 1.5 h. Then raise the temperature to 85 °C, distill off the ethanol, and calcine the substrate at 930 °C under nitrogen protection for 2.5 h to obtain modified carbon black;

[0060] Step B3: Disperse the modified carbon black in tetrahydrofuran, add KH560, and under the conditions of a rotation speed of 150 r / min, a temperature of 25 °C, and an alkaline condition, react for 4 h. Then add KH550, raise the temperature to 65 °C, and react for 15 h. Cool to room temperature, add ammonium fluoride, and continue stirring for 23 h. Filter to remove the filtrate to obtain a modified matrix;

[0061] Step B4: Disperse the modified matrix in toluene, add p-toluenesulfonic acid, and under the conditions of a rotation speed of 150 r / min and a temperature of 115 °C, stir and add maleic anhydride, and react for 2 - 3 h. Filter to remove the filtrate to obtain conductive particles.

[0062] The dosage ratio of the carbon black, acetic acid, and KH550 described in Step B1 is 1 g:1 mL:6.5 mg.

[0063] The dosage ratio of the pretreated carbon black, ferric nitrate nonahydrate, and sodium dodecylbenzenesulfonate described in Step B2 is 1 g:185 mg:40 mg.

[0064] The dosage ratio of the modified matrix, KH560, KH550, and ammonium fluoride described in Step B3 is 1 g:1.1 mL:3 mL:0.3 g.

[0065] The dosage ratio of the amino group, maleic anhydride, and p-toluenesulfonic acid on the modified matrix described in Step B4 is 1 mol:1.3 mol:6.4 g.

[0066] Example 3

[0067] A preparation method of a polyolefin plastic pipe specifically includes the following steps:

[0068] Mix the modified additive, conductive particles, dicumyl peroxide, and LLDPE, add them to a twin-screw extruder, and under the conditions of temperatures of 120 °C, 130 °C, 150 °C, 180 °C, and 160 °C in sequence, extrude and shape and cool to obtain a polyolefin plastic pipe.

[0069] The mass ratio of the modified additive, conductive particles, dicumyl peroxide, and LLDPE is 13:25:0.5:100, and the model of LLDPE is 7042.

[0070] The modified additive is prepared by the following steps:

[0071] Step A1: Disperse Y-aminopropylmethyldiethoxysilane in toluene, add p-toluenesulfonic acid, stir and add maleic anhydride at a rotation speed of 200 r / min and a temperature of 115 °C, and react for 6 h to obtain Intermediate 1. Add Intermediate 1 to deionized water, stir at a rotation speed of 300 r / min and a temperature of 30 °C for 5 min, then add tetrahydrofuran and concentrated sulfuric acid, raise the temperature to 65 °C, keep warm for 10 min, add D4 and 1,1,3,3-tetramethyldisiloxane, and react for 5 h to obtain polysiloxane;

[0072] Step A2: Mix the polysiloxane and the benzene solution of acrylic acid, stir and add chloroplatinic acid at a rotation speed of 300 r / min and a temperature of 60 °C. After adding, raise the temperature to 65 °C and react for 4 h to obtain Intermediate 2. Mix Intermediate 2, oxalyl chloride, dichloromethane and N,N-dimethylformamide, react at a rotation speed of 200 r / min and a temperature of 25 °C for 2 h, then add ammonia water and continue to react for 40 min to obtain amide-capped polysiloxane;

[0073] Step A3: Mix the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran and glacial acetic acid evenly, react at a rotation speed of 200 r / min and a temperature of 105 °C for 6 h to obtain modified polysiloxane. Dissolve the modified polysiloxane in toluene, stir and add ferric chloride hexahydrate and pyrrole at a rotation speed of 300 r / min and a temperature of 25 °C, and react for 25 h to obtain modified additive.

[0074] The dosage ratio of Y-aminopropylmethyldiethoxysilane, p-toluenesulfonic acid and maleic anhydride described in Step A1 is 1 mL: 1.3 mL: 7.1 g, and the dosage ratio of Intermediate 1, deionized water, D4 and 1,1,3,3-tetramethyldisiloxane is 10 mmol: 2 mL: 1 mmol: 8 mmol. The dosage of concentrated sulfuric acid is 5% of the sum of the masses of Intermediate 1, D4 and 1,1,3,3-tetramethyldisiloxane.

[0075] The molar ratio of the polysiloxane and acrylic acid described in Step A2 is 1:2, the dosage of chloroplatinic acid is 0.03‰ of the mass of acrylic acid, and the dosage ratio of Intermediate 2, oxalyl chloride, dichloromethane, N,N-dimethylformamide and ammonia water is 40 mmol: 60 mL: 140 mmol: 0.15 mL: 45 mL.

[0076] The dosage ratio of the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran and glacial acetic acid described in Step A3 is 3 mmol: 3 mmol: 4 mL, and the molar ratio of the modified polysiloxane, ferric chloride hexahydrate and pyrrole is 3:4:10.

[0077] The conductive particles are prepared by the following steps:

[0078] Step B1: Put carbon black into a high-temperature atmosphere furnace, introduce nitrogen, increase the temperature to 1000 °C at a heating rate of 5 °C / min, introduce carbon dioxide, keep the temperature for 3 h, cool to room temperature, disperse in ethanol, add acetic acid and KH550, and stir at a rotation speed of 300 r / min and a temperature of 25 °C for 40 min, then increase the temperature to 85 °C and continue stirring for 5 h to obtain pretreated carbon black;

[0079] Step B2: Disperse the pretreated carbon black in ethanol, add ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate, and perform ultrasonic treatment for 1.5 h under the conditions of a frequency of 30 kHz, a temperature of 25 °C, and an alkaline condition, then increase the temperature to 85 °C, distill off ethanol, and calcine the substrate at 950 °C under nitrogen protection for 3 h to obtain modified carbon black;

[0080] Step B3: Disperse the modified carbon black in tetrahydrofuran, add KH560, and react for 5 h under the conditions of a rotation speed of 200 r / min, a temperature of 25 °C, and an alkaline condition, then add KH550, increase the temperature to 70 °C, and react for 15 h, cool to room temperature, add ammonium fluoride, and continue stirring for 25 h, filter to remove the filtrate to obtain a modified matrix;

[0081] Step B4: Disperse the modified matrix in toluene, add p-toluenesulfonic acid, stir and add maleic anhydride at a rotation speed of 200 r / min and a temperature of 115 °C, and react for 2 - 3 h, filter to remove the filtrate to obtain conductive particles.

[0082] The dosage ratio of the carbon black, acetic acid and KH550 described in Step B1 is 1 g:1 mL:6.5 mg.

[0083] The dosage ratio of the pretreated carbon black, ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate described in Step B2 is 1 g:185 mg:40 mg.

[0084] The dosage ratio of the modified matrix, KH560, KH550 and ammonium fluoride described in Step B3 is 1 g:1.1 mL:3 mL:0.3 g.

[0085] The dosage ratio of the amino group, maleic anhydride and p-toluenesulfonic acid on the modified matrix described in Step B4 is 1 mol:1.3 mol:6.4 g.

[0086] Comparative Example 1

[0087] In this comparative example, compared with Example 1, modified carbon black is used instead of conductive particles, and the other steps are the same.

[0088] Comparative Example 2

[0089] In this comparative example, no modified additive was added compared with Example 1, and the remaining steps were the same.

[0090] The materials prepared in Examples 1-3 and Comparative Examples 1-2 were made into Type 1A specimens in GB / T 1040.2-2006, and the tensile strength and elongation at break were detected under the condition of a tensile speed of 100 mm / min.

[0091] The surface resistance of the materials prepared in Examples 1-3 and Comparative Examples 1-2 was detected according to the standard of GB / T 1410-2016, and the results are shown in the following table.

[0092]

[0093]

[0094] It can be seen from the above table that this application has good mechanical effects and excellent electrical conductivity.

[0095] The above content is only an example and explanation of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all belong to the protection scope of the present invention.

Claims

1. A method for preparing a polyolefin plastic pipe, characterized in that: Specifically, it includes the following steps: Mix the modified additive, conductive particles, dicumyl peroxide, and LLDPE, extrude and shape them, and then cool to obtain a polymer polyolefin plastic pipe; The modified additive is prepared by the following steps: Step A1: Disperse γ-aminopropylmethyldiethoxysilane in toluene, add p-toluenesulfonic acid, stir, and add maleic anhydride, and react to obtain Intermediate 1. Add Intermediate 1 to deionized water, stir, add tetrahydrofuran and concentrated sulfuric acid, raise the temperature and keep it warm, add D4 and 1,1,3,3-tetramethyldihydroxydisiloxane, and react to obtain polysiloxane; Step A2: Mix and stir the polysiloxane and a benzene solution of acrylic acid, add chloroplatinic acid, and raise the temperature for reaction after addition to obtain Intermediate 2. Mix Intermediate 2, oxalyl chloride, dichloromethane, and N,N-dimethylformamide for reaction, then add ammonia water and continue the reaction to obtain amide-capped polysiloxane; Step A3: Mix and react the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran, and glacial acetic acid to obtain modified polysiloxane. Dissolve the modified polysiloxane in toluene, stir, add ferric chloride hexahydrate and pyrrole, and react to obtain the modified additive; The conductive particles are prepared by the following steps: Step B1: Put carbon black into a high-temperature atmosphere furnace, introduce nitrogen, raise the temperature, then introduce carbon dioxide, keep it warm, cool to room temperature, disperse it in ethanol, add acetic acid and KH550, stir, raise the temperature and continue stirring to obtain pretreated carbon black; Step B2: Disperse the pretreated carbon black in ethanol, add ferric nitrate nonahydrate and sodium dodecylbenzenesulfonate, perform ultrasonic treatment, distill off ethanol, and calcine the substrate to obtain modified carbon black; Step B3: Disperse the modified carbon black in tetrahydrofuran, add KH560 for reaction, then add KH550, raise the temperature and continue the reaction, cool to room temperature, add ammonium fluoride, continue stirring, and filter to remove the filtrate to obtain a modified matrix; Step B4: Disperse the modified matrix in toluene, add p-toluenesulfonic acid, stir, add maleic anhydride, and react, then filter to remove the filtrate to obtain conductive particles.

2. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of γ-aminopropylmethyldiethoxysilane, p-toluenesulfonic acid, and maleic anhydride in Step A1 is 1 mL:1.3 mL:7.1 g, and the dosage ratio of Intermediate 1, deionized water, D4, and 1,1,3,3-tetramethyldihydroxydisiloxane is 10 mmol:2 mL:1 mmol:8 mmol. The dosage of concentrated sulfuric acid is 3-5% of the sum of the masses of Intermediate 1, D4, and 1,1,3,3-tetramethyldihydroxydisiloxane.

3. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The molar ratio of polysiloxane and acrylic acid in Step A2 is 1:2, the dosage of chloroplatinic acid is 0.01-0.03‰ of the mass of acrylic acid, and the dosage ratio of Intermediate 2, oxalyl chloride, dichloromethane, N,N-dimethylformamide, and ammonia water is 40 mmol:60 mL:140 mmol:0.15 mL:45 mL.

4. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of the amide-capped modified polysiloxane, 2,5-dimethoxytetrahydrofuran, and glacial acetic acid described in step A3 is 3 mmol: 3 mmol: 4 mL, and the molar ratio of the modified polysiloxane, ferric chloride hexahydrate, and pyrrole is 3: 4:

10.

5. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of the carbon black, acetic acid, and KH550 described in step B1 is 1 g: 1 mL: 6.5 mg.

6. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of the pretreated carbon black, ferric nitrate nonahydrate, and sodium dodecylbenzenesulfonate in step B2 is 1 g: 185 mg: 40 mg.

7. The preparation method of a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of the modified carbon black, KH560, KH550, and ammonium fluoride described in step B3 is 1 g: 1.1 mL: 3 mL: 0.3 g.

8. A method for preparing a polyolefin plastic pipe according to claim 1, characterized in that: The dosage ratio of the amino group, maleic anhydride, and p-toluenesulfonic acid on the modified matrix described in step B4 is 1 mol: 1.3 mol: 6.4 g.

9. A polyolefin plastic pipe, characterized in that: Prepared by the preparation method according to any one of claims 1-8.

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