High-wear-resistance Krah pipe and preparation method thereof

Abstract

The invention discloses a high-wear-resistance Krah pipe and a preparation method thereof, and relates to the technical field of wear-resistant pipe preparation, the high-wear-resistance Krah pipe is prepared by weighing the following raw materials in parts by weight: 100-120 parts of modified polyethylene, 30-50 parts of modified resin, 20-30 parts of modified cellulose, 5-8 parts of a cross-linking agent and 0.5-1 part of p-toluenesulfonic acid, and carrying out melt blending, according to the high-wear-resistance Krah pipe, the modified resin and the modified cellulose are synchronously wound on a heated mold together with a corrugated pipe reinforcing rib coated with PP, a pipe is formed, the high-wear-resistance Krah pipe is prepared, when the raw materials are melted and blended, under the action of p-toluenesulfonic acid, phenylboronic acid of a side chain of the modified resin and phenylboronic acid of a side chain of the modified cellulose can react with a diol group on a cross-linking agent to form boric acid ester, and therefore the high-wear-resistance Krah pipe is obtained. And in a high-temperature molten state, the modified polyethylene, the modified resin and the modified cellulose are fully mixed to form a three-dimensional dynamic cross-linked structure, and the dynamic cross-linked structure can disperse stress, inhibit cracks and self-repair the structure, so that the stability of the material in the friction process is enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of wear-resistant pipe preparation, and particularly relates to a highly wear-resistant corrugated pipe and a preparation method thereof. Background Art

[0002] The high-density polyethylene wound structured-wall pipe (corrugated pipe) is made of high-density polyethylene resin (HDPE) as raw material and produced by a hot winding forming process. The high-density polyethylene wound structured-wall pipe is a new type of special-shaped structured-wall pipe and an environmentally friendly and safe product, which has the advantages of light weight, strong pressure-bearing capacity, high interface quality, long service life, corrosion resistance, high ring stiffness, and convenient construction. It is widely used in hotspots such as municipal engineering, nuclear power and thermal power, petrochemical industry, wharf drainage (including rainwater and sewage), deep-sea sewage discharge in coastal cities, and large-scale water diversion. However, after long-term use, the high-density polyethylene on the surface of the corrugated pipe will be worn, and serious wear will lead to an increase in the inner wall roughness, affecting the fluid transportation efficiency. Long-term wear may accelerate aging and corrosion, shortening the service life of the pipeline. Summary of the Invention

[0003] The purpose of the present invention is to provide a highly wear-resistant corrugated pipe and a preparation method thereof, which solves the problem that the surface of the corrugated pipe is seriously worn after long-term use, increasing potential safety hazards.

[0004] The purpose of the present invention can be achieved by the following technical solutions: A preparation method of a highly wear-resistant corrugated pipe specifically includes the following steps: Step A1: Mix high-density polyethylene, acryloyl chloride, and diisopropylbenzene peroxide, and carry out a melting reaction at a temperature of 180 - 200 °C for 15 - 20 min to obtain pretreated polyethylene. Mix the pretreated polyethylene and n-hexane evenly, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 0 - 3 °C, stir and add triethylamine and maleimide, and then raise the temperature to 20 - 25 °C for a reaction of 3 - 4 h to obtain modified polyethylene; Step A2: Mix carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, and dichloromethane evenly, and under the conditions of a rotation speed of 60 - 80 r / min and a temperature of 40 - 45 °C, stir and add cetyltrimethylammonium bromide for a reaction of 20 - 25 h to obtain pretreated cellulose. Mix the pretreated cellulose, 4-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide evenly, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 20 - 25 °C, carry out a reaction of 20 - 25 h to obtain modified cellulose; Step A3: Weigh the following raw materials in parts by weight: 100 - 120 parts of modified polyethylene, 30 - 50 parts of modified resin, 20 - 30 parts of modified cellulose, 5 - 8 parts of crosslinking agent, and 0.5 - 1 part of p-toluenesulfonic acid. Under the condition of a temperature of 190 - 200 °C, heat and mix the raw materials for 5 - 10 min, and then synchronously wind them with the corrugated pipe reinforcement coated with PP on a heated mold to form a pipe, thus obtaining a highly wear-resistant corrugated pipe.

[0005] Furthermore, the mass ratio of the high-density polyethylene, acryloyl chloride, and diisopropylbenzene peroxide in Step A1 is 95:5:1, and the molar ratio of the acyl chloride, triethylamine, and maleimide on the pretreated polyethylene is 1:1.1:1.

[0006] Furthermore, the dosage ratio of the carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, dichloromethane, and cetyltrimethylammonium bromide in Step A2 is 1 g:40 mL:8 g:40 mL:6 mmol, the mass fraction of the sodium hydroxide solution is 4%, and the dosage ratio of the pretreated cellulose, p-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide is 1 g:5 mol:100 mL:5 mol:5 mol.

[0007] Furthermore, the modified resin is prepared by the following steps: Step B1: Mix 4,4'-biphenol, toluene, and glacial acetic acid evenly. Under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 0 °C, stir and add concentrated nitric acid, and carry out the reaction for 2 - 4 h to obtain a modified monomer. Mix the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane, and toluene evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 170 - 180 °C, carry out the reaction for 1 - 1.5 h, then raise the temperature to 200 - 210 °C and carry out the reaction for 3 - 4 h to obtain modified polyether ether ketone; Step B2: Mix the modified polyether ether ketone, triethylamine, and xylene evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 50 - 60 °C, stir and add furan carbonyl chloride, and carry out the reaction for 3 - 5 h to obtain pretreated polyether ether ketone. Mix the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine, and toluene evenly, introduce hydrogen to keep the pressure at 0.5 - 1 MPa, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 40 - 50 °C, carry out the reaction for 3 - 5 h to obtain functionalized polyether ether ketone; Step B3: Mix the functionalized polyether ether ketone, 4-formylphenylboronic acid, 3A molecular sieve, and xylene, and carry out the reaction for 2 - 3 h under the conditions of a rotation speed of 150 - 200 r / min, a temperature of 20 - 25 °C, and a pH value of 5 - 6 to obtain the modified resin.

[0008] Furthermore, the dosage ratio of 4,4'-biphenol, toluene, glacial acetic acid, and concentrated nitric acid described in Step B1 is 10 mmol: 10 mL: 12 mL: 1.5 mL, the mass fraction of concentrated nitric acid is 68%, and the dosage ratio of the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane, and toluene is 10 mmol: 30 mmol: 21 mmol: 20 mmol: 12 mmol: 35 mL: 10 mL.

[0009] Furthermore, the molar ratio of the hydroxyl group on the modified polyether ether ketone, triethylamine, and furan carbonyl chloride described in Step B2 is 1: 1.2: 1, and the dosage ratio of the nitro group on the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine, and toluene is 10 mmol: 200 mg: 1 mg: 60 mL.

[0010] Furthermore, the dosage ratio of the amino group on the functionalized polyether ether ketone, 4-formylphenylboronic acid, and 3A molecular sieve described in Step B3 is 1 mol: 1 mol: 100 g.

[0011] Furthermore, the crosslinking agent is prepared by the following steps: Mix pentaerythritol tetra(3-mercaptopropionate), butanediol, benzophenone, and dimethyl sulfoxide evenly, and carry out the reaction for 20 - 30 min under the conditions of a rotation speed of 150 - 200 r / min, a temperature of 20 - 25 °C, and irradiation with 365 nm ultraviolet light to obtain the crosslinking agent.

[0012] Furthermore, the molar ratio of pentaerythritol tetra(3-mercaptopropionate) and butanediol is 1: 4, and the dosage of benzophenone is 1% of the sum of the masses of pentaerythritol tetra(3-mercaptopropionate) and butanediol.

[0013] The beneficial effects of the present invention: A highly wear-resistant corrugated pipe disclosed by the present invention melts and blends the raw materials modified polyethylene, modified resin, modified cellulose, crosslinking agent, and p-toluenesulfonic acid, and then synchronously winds them with a corrugated pipe reinforcing rib coated with PP on a heated mold to form a pipe, thereby obtaining the highly wear-resistant corrugated pipe. The modified polyethylene uses high-density polyethylene as the raw material, and under the action of diisopropylbenzene peroxide, the double bond on acryloyl chloride is grafted onto the high-density polyethylene molecular chain to obtain the pretreated polyethylene. The pretreated polyethylene and maleimide react under the action of triethylamine, so that the acyl chloride on the pretreated polyethylene reacts with the imine on maleimide to obtain the modified polyethylene.

[0014] The modified cellulose uses carboxymethyl cellulose and furan carbonyl chloride as raw materials, making the acyl chloride on the furan carbonyl chloride react with the hydroxyl groups on the carboxymethyl cellulose to obtain the pretreated cellulose. Then, the pretreated cellulose reacts with 4-aminophenylboronic acid, causing the carboxyl groups on the pretreated cellulose to undergo a dehydration reaction with the amino groups on the 4-aminophenylboronic acid to obtain the modified cellulose.

[0015] The modified resin uses 4,4'-biphenol as a raw material and is treated with concentrated nitric acid to nitrify the ortho positions of the phenolic hydroxyl groups on the 4,4'-biphenol to obtain the modified monomer. The modified monomer, 4,4'-difluorobenzophenone, and bisphenol A react to form a polyether ether ketone structure to obtain the modified polyether ether ketone. The modified polyether ether ketone reacts with furan carbonyl chloride, causing the phenolic hydroxyl groups at both ends of the modified polyether ether ketone to react with the acyl chloride on the furan carbonyl chloride to obtain the pretreated polyether ether ketone. The pretreated polyether ether ketone is reduced under a hydrogen atmosphere using a palladium-carbon catalyst, causing the nitro groups on the molecular chain to be converted into amino groups to obtain the functionalized polyether ether ketone. The functionalized polyether ether ketone reacts with 4-formylphenylboronic acid, causing the amino groups on the functionalized polyether ether ketone to react with the aldehyde groups on the 4-formylphenylboronic acid to obtain the modified resin.

[0016] The crosslinking agent uses pentaerythritol tetra(3-mercaptopropionate) and butenediol as raw materials and reacts under ultraviolet light irradiation under the action of benzophenone, causing the mercapto groups on the pentaerythritol tetra(3-mercaptopropionate) to react with the double bonds on the butenediol to obtain the crosslinking agent.

[0017] When the raw materials are melt-blended, under the action of p-toluenesulfonic acid, the phenylboronic acid on the side chain of the modified resin and the phenylboronic acid on the side chain of the modified cellulose can react with the diol groups on the crosslinking agent to form borate esters. And in the high-temperature molten state, the modified polyethylene, modified resin, and modified cellulose are fully mixed. During the cooling process, the furan groups at both ends of the modified resin molecular chain and the furan groups on the side chain of the modified cellulose can react with the maleimide group DA on the side chain of the modified polyethylene molecule and cooperate with the carbon-nitrogen double bond in the modified resin to form a three-dimensional dynamic crosslinking structure. The dynamic crosslinking structure can disperse stress, inhibit cracks, and self-repair the structure, thereby enhancing the stability of the material during the friction process. The cellulose can form a rigid network in the matrix material, effectively resisting the crack propagation caused by external forces, and further improving the wear resistance of the surface of the corrugated pipe. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0019] Figure 1 It is the electron microscope of the fracture surface in Embodiment 1 of the present invention.

[0020] Figure 2 SEM of the fracture surface of Comparative Example 1 in the present invention.

[0021] Figure 3 SEM of the fracture surface of Comparative Example 2 in the present invention.

[0022] Figure 4 SEM of the fracture surface of Comparative Example 3 in the present invention.

[0023] Figure 5 SEM of the fracture surface of Comparative Example 4 in the present invention. Detailed implementation manners

[0024] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. 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.

[0025] As Figures 1 to 5 shown, in Embodiment 1, a preparation method of a highly wear-resistant corrugated pipe specifically includes the following steps: Step A1: Mix high-density polyethylene, acryloyl chloride, and diisopropylbenzene peroxide, and carry out a melting reaction at a temperature of 180 °C for 15 min to obtain pretreated polyethylene. Mix the pretreated polyethylene and n-hexane evenly, and under the conditions of a rotation speed of 120 r / min and a temperature of 0 °C, stir and add triethylamine and maleimide, and then raise the temperature to 20 °C and react for 3 h to obtain modified polyethylene. Step A2: Mix carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, and dichloromethane evenly, and under the conditions of a rotation speed of 60 r / min and a temperature of 40 °C, stir and add cetyltrimethylammonium bromide, and react for 20 h to obtain pretreated cellulose. Mix the pretreated cellulose, p-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide evenly, and under the conditions of a rotation speed of 120 r / min and a temperature of 20 °C, react for 20 h to obtain modified cellulose. Step A3: Weigh the following raw materials in parts by weight: 100 parts of modified polyethylene, 30 parts of modified resin, 20 parts of modified cellulose, 5 parts of cross-linking agent, and 0.5 part of p-toluenesulfonic acid. Heat and mix the raw materials at a temperature of 190 °C for 5 min, and then synchronously wind them with the corrugated pipe reinforcing rib coated with PP on a heated mold to form a pipe, thereby obtaining a highly wear-resistant corrugated pipe.

[0026] The mass ratio of high-density polyethylene, acryloyl chloride, and diisopropylbenzene peroxide described in step A1 is 95:5:1. The molar ratio of acyl chloride, triethylamine, and maleimide on the pretreated polyethylene is 1:1.1:1. The melt index of high-density polyethylene is 1.0 g / 10 min.

[0027] The dosage ratio of carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, dichloromethane, and cetyltrimethylammonium bromide described in step A2 is 1 g:40 mL:8 g:40 mL:6 mmol. The mass fraction of the sodium hydroxide solution is 4%. The molecular weight of carboxymethyl cellulose M.W. is 90,000, the degree of substitution DS = 0.7, and the viscosity is 50 mPa·s. The dosage ratio of pretreated cellulose, 4-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide is 1 g:5 mol:100 mL:5 mol:5 mol. The pH value of the MES buffer solution is 5.5, and the concentration is 0.01 mol / L.

[0028] The modified resin is prepared by the following steps: Step B1: Mix 4,4'-biphenol, toluene, and glacial acetic acid evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 0 °C, stir and add concentrated nitric acid, and react for 2 h to obtain a modified monomer. Mix the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane, and toluene evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 200 r / min and a temperature of 170 °C, react for 1 h, then raise the temperature to 200 °C and react for 3 h to obtain modified polyether ether ketone; Step B2: Mix the modified polyether ether ketone, triethylamine, and xylene evenly, introduce nitrogen protection, and under the conditions of a rotation speed of 150 r / min and a temperature of 50 °C, stir and add furan carbonyl chloride, and react for 3 h to obtain pretreated polyether ether ketone. Mix the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine, and toluene evenly, introduce hydrogen to maintain a pressure of 0.5 MPa, and under the conditions of a rotation speed of 120 r / min and a temperature of 40 °C, react for 3 h to obtain functionalized polyether ether ketone; Step B3: Mix the functionalized polyether ether ketone, 4-formylphenylboronic acid, 3A molecular sieve, and xylene, and under the conditions of a rotation speed of 150 r / min, a temperature of 20 °C, and a pH value of 5, react for 2 h to obtain the modified resin.

[0029] The dosage ratio of 4,4'-biphenol, toluene, glacial acetic acid and concentrated nitric acid described in step B1 is 10 mmol: 10 mL: 12 mL: 1.5 mL, the mass fraction of concentrated nitric acid is 68%, and the dosage ratio of the modifying monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane and toluene is 10 mmol: 30 mmol: 21 mmol: 20 mmol: 12 mmol: 35 mL: 10 mL.

[0030] The molar ratio of the hydroxyl group on the modified polyetheretherketone, triethylamine and furan carbonyl chloride described in step B2 is 1: 1.2: 1, and the dosage ratio of the nitro group on the pretreated polyetheretherketone, palladium-carbon catalyst, triethylamine and toluene is 10 mmol: 200 mg: 1 mg: 60 mL.

[0031] The dosage ratio of the amino group on the functionalized polyetheretherketone, 4-formylphenylboronic acid and 3A molecular sieve described in step B3 is 1 mol: 1 mol: 100 g.

[0032] The crosslinking agent is prepared by the following steps: Mix pentaerythritol tetra(3-mercaptopropionate), butanediol, benzophenone and dimethyl sulfoxide evenly, and carry out a reaction for 20 min under the conditions of a rotation speed of 150 r / min, a temperature of 20 °C and ultraviolet light irradiation at 365 nm to obtain the crosslinking agent.

[0033] The molar ratio of pentaerythritol tetra(3-mercaptopropionate) to butanediol is 1: 4, and the dosage of benzophenone is 1% of the sum of the masses of pentaerythritol tetra(3-mercaptopropionate) and butanediol.

[0034] Example 2, a preparation method of a highly wear-resistant corrugated pipe, specifically includes the following steps: Step A1: Mix high-density polyethylene, acryloyl chloride and diisopropyl peroxide, and carry out a melting reaction for 18 min under the condition of a temperature of 190 °C to obtain pretreated polyethylene. Mix the pretreated polyethylene and n-hexane evenly, stir and add triethylamine and maleimide under the conditions of a rotation speed of 120 r / min and a temperature of 3 °C, and raise the temperature to 20 °C for a reaction of 4 h to obtain modified polyethylene; Step A2: Mix carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride and dichloromethane evenly, stir and add cetyltrimethylammonium bromide under the conditions of a rotation speed of 60 r / min and a temperature of 45 °C for a reaction of 20 h to obtain pretreated cellulose. Mix the pretreated cellulose, p-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide evenly, and carry out a reaction for 25 h under the conditions of a rotation speed of 150 r / min and a temperature of 20 °C to obtain modified cellulose; Step A3: Weigh the following raw materials in parts by weight: 110 parts of modified polyethylene, 40 parts of modified resin, 25 parts of modified cellulose, 6.5 parts of cross-linking agent and 0.8 parts of p-toluenesulfonic acid, heat and mix the raw materials at a temperature of 200° C. for 8 minutes, and then wind them together with the corrugated pipe reinforcement rib coated with PP on a heated mold to form a pipe to obtain a high wear-resistant carat pipe.

[0035] The mass ratio of the high-density polyethylene, acryloyl chloride and diisopropylbenzene peroxide described in step A1 is 95:5:1, the molar ratio of acyl chloride, triethylamine and maleimide on the pretreated polyethylene is 1:1.1:1, and the melt index of the high-density polyethylene is 1.0 g / 10 min.

[0036] The amount ratio of carboxymethyl cellulose, sodium hydroxide solution, furanyl chloride, dichloromethane and hexadecyltrimethylammonium bromide described in step A2 is 1g:40mL:8g:40mL:6mmol, the mass fraction of sodium hydroxide solution is 4%, the molecular weight of carboxymethyl cellulose is MW90000, the degree of substitution DS=0.7, the viscosity is 50mPa.s, the amount ratio of pretreated cellulose, p-aminophenylboronic acid, MES buffer, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide is 1g:5mol:100mL:5mol:5mol, the pH value of MES buffer is 5.5, and the concentration is 0.01mol / L.

[0037] The modified resin is prepared by the following steps: Step B1: 4,4'-biphenol, toluene and glacial acetic acid are mixed evenly, stirred and concentrated nitric acid is added at a speed of 150 r / min and a temperature of 0°C, and the reaction is carried out for 3 hours to obtain a modified monomer, and the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, cyclopentane sulfone and toluene are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 175°C for 1.5 hours, and then the temperature is raised to 205°C and the reaction is carried out for 4 hours to obtain a modified polyetheretherketone; Step B2: uniformly mix the modified polyetheretherketone, triethylamine and xylene, introduce nitrogen protection, stir and add furancarbonyl chloride at a speed of 150 r / min and a temperature of 55°C, and react for 4 hours to obtain pretreated polyetheretherketone; uniformly mix the pretreated polyetheretherketone, palladium carbon catalyst, triethylamine and toluene, introduce hydrogen to maintain the pressure at 0.8 MPa, and react for 4 hours at a speed of 150 r / min and a temperature of 45°C to obtain functionalized polyetheretherketone; Step B3: Mix functionalized polyether ether ketone, 4-formylphenylboronic acid, 3A molecular sieve and xylene, and react for 3 h under the conditions of a rotation speed of 150 r / min, a temperature of 25 °C, and a pH value of 5 to obtain a modified resin.

[0038] The dosage ratios of 4,4'-biphenol, toluene, glacial acetic acid and concentrated nitric acid described in Step B1 are 10 mmol: 10 mL: 12 mL: 1.5 mL, the mass fraction of concentrated nitric acid is 68%, and the dosage ratios of the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane and toluene are 10 mmol: 30 mmol: 21 mmol: 20 mmol: 12 mmol: 35 mL: 10 mL.

[0039] The molar ratio of the hydroxyl group on the modified polyether ether ketone, triethylamine and furan carbonyl chloride described in Step B2 is 1: 1.2: 1, and the dosage ratios of the nitro group on the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine and toluene are 10 mmol: 200 mg: 1 mg: 60 mL.

[0040] The dosage ratios of the amino group on the functionalized polyether ether ketone, 4-formylphenylboronic acid and 3A molecular sieve described in Step B3 are 1 mol: 1 mol: 100 g.

[0041] The crosslinking agent is prepared by the following steps: Mix pentaerythritol tetra(3-mercaptopropionate), butanediol, benzophenone and dimethyl sulfoxide evenly, and react for 25 min under the conditions of a rotation speed of 150 r / min, a temperature of 25 °C, and irradiation with 365 nm ultraviolet light to obtain a crosslinking agent.

[0042] The molar ratio of pentaerythritol tetra(3-mercaptopropionate) to butanediol is 1: 4, and the dosage of benzophenone is 1% of the sum of the masses of pentaerythritol tetra(3-mercaptopropionate) and butanediol.

[0043] Example 3, a preparation method of a highly wear-resistant corrugated pipe, specifically includes the following steps: Step A1: Mix high-density polyethylene, acryloyl chloride and diisopropylbenzene peroxide, and carry out a melting reaction for 20 min under the condition of a temperature of 200 °C to obtain pretreated polyethylene. Mix the pretreated polyethylene and n-hexane evenly, stir and add triethylamine and maleimide under the conditions of a rotation speed of 150 r / min and a temperature of 3 °C, and raise the temperature to 25 °C and react for 4 h to obtain modified polyethylene; Step A2: Mix carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, and dichloromethane evenly. Under the conditions of a rotation speed of 80 r / min and a temperature of 45 °C, stir and add cetyltrimethylammonium bromide, and react for 25 h to obtain pretreated cellulose. Mix the pretreated cellulose, 4-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide evenly, and react for 25 h under the conditions of a rotation speed of 150 r / min and a temperature of 25 °C to obtain modified cellulose; Step A3: Weigh the following raw materials in parts by weight: 120 parts of modified polyethylene, 50 parts of modified resin, 30 parts of modified cellulose, 8 parts of crosslinking agent, and 1 part of p-toluenesulfonic acid. Heat and mix the raw materials at a temperature of 200 °C for 10 min, and then wind them synchronously with the corrugated pipe reinforcing rib coated with PP on a heated mold to form a pipe, thus obtaining a highly wear-resistant corrugated pipe.

[0044] The mass ratio of the high-density polyethylene, acryloyl chloride, and diisopropylbenzene peroxide described in Step A1 is 95:5:1. The molar ratio of the acyl chloride, triethylamine, and maleimide on the pretreated polyethylene is 1:1.1:1. The melt index of the high-density polyethylene is 1.0 g / 10 min.

[0045] The dosage ratio of the carboxymethyl cellulose, sodium hydroxide solution, furan carbonyl chloride, dichloromethane, and cetyltrimethylammonium bromide described in Step A2 is 1 g:40 mL:8 g:40 mL:6 mmol. The mass fraction of the sodium hydroxide solution is 4%. The molecular weight M.W. of the carboxymethyl cellulose is 90000, the degree of substitution DS = 0.7, and the viscosity is 50 mPa·s. The dosage ratio of the pretreated cellulose, 4-aminophenylboronic acid, MES buffer solution, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide is 1 g:5 mol:100 mL:5 mol:5 mol. The pH value of the MES buffer solution is 5.5, and the concentration is 0.01 mol / L.

[0046] The described modified resin is prepared by the following steps: Step B1: Mix 4,4'-biphenol, toluene, and glacial acetic acid evenly. Under the conditions of a rotation speed of 200 r / min and a temperature of 0 °C, stir and add concentrated nitric acid, and react for 4 h to obtain a modified monomer. Mix the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane, and toluene evenly, introduce nitrogen protection, and react at a rotation speed of 300 r / min and a temperature of 180 °C for 1.5 h, then raise the temperature to 210 °C and react for 4 h to obtain modified polyetheretherketone; Step B2: Mix the modified polyether ether ketone, triethylamine, and xylene evenly, introduce nitrogen for protection, stir and add furan carbonyl chloride under the conditions of a rotation speed of 200 r / min and a temperature of 60 °C, and react for 5 h to obtain pretreated polyether ether ketone. Then mix the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine, and toluene evenly, introduce hydrogen to maintain a pressure of 1 MPa, and react for 5 h under the conditions of a rotation speed of 150 r / min and a temperature of 50 °C to obtain functionalized polyether ether ketone; Step B3: Mix the functionalized polyether ether ketone, 4-formylphenylboronic acid, 3A molecular sieve, and xylene, and react for 3 h under the conditions of a rotation speed of 200 r / min, a temperature of 25 °C, and a pH value of 6 to obtain a modified resin.

[0047] The dosage ratio of 4,4'-biphenol, toluene, glacial acetic acid, and concentrated nitric acid described in Step B1 is 10 mmol: 10 mL: 12 mL: 1.5 mL, the mass fraction of concentrated nitric acid is 68%, and the dosage ratio of the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, sulfolane, and toluene is 10 mmol: 30 mmol: 21 mmol: 20 mmol: 12 mmol: 35 mL: 10 mL.

[0048] The molar ratio of the hydroxyl group on the modified polyether ether ketone, triethylamine, and furan carbonyl chloride described in Step B2 is 1: 1.2: 1, and the dosage ratio of the nitro group on the pretreated polyether ether ketone, palladium-carbon catalyst, triethylamine, and toluene is 10 mmol: 200 mg: 1 mg: 60 mL.

[0049] The dosage ratio of the amino group on the functionalized polyether ether ketone, 4-formylphenylboronic acid, and 3A molecular sieve described in Step B3 is 1 mol: 1 mol: 100 g.

[0050] The crosslinking agent is prepared by the following steps: Mix pentaerythritol tetra(3-mercaptopropionate), butanediol, benzophenone, and dimethyl sulfoxide evenly, and react for 30 min under the conditions of a rotation speed of 200 r / min, a temperature of 25 °C, and irradiation with 365 nm ultraviolet light to obtain a crosslinking agent.

[0051] The molar ratio of pentaerythritol tetra(3-mercaptopropionate) and butanediol is 1: 4, and the dosage of benzophenone is 1% of the sum of the masses of pentaerythritol tetra(3-mercaptopropionate) and butanediol.

[0052] Comparative Example 1: In this comparative example, cellulose is used instead of modified cellulose compared with Example 1, and the remaining steps are the same.

[0053] Comparative Example 2: In this comparative example, modified cellulose is not added compared with Example 1, and the remaining steps are the same.

[0054] Comparative Example 3: Compared with Example 1, functionalized polyether ether ketone was used instead of the modified resin in this comparative example, and the remaining steps were the same.

[0055] Comparative Example 4: Compared with Example 1, modified polyether ether ketone was used instead of the modified resin in this comparative example, and the remaining steps were the same.

[0056] Flat specimens with a thickness of 4 mm were prepared from the materials obtained in Examples 1 - 3 and Comparative Examples 1 - 4. Using a wear testing machine, an H-18 grinding wheel, applying a load of 800 g, a rotational speed of 60 r / min, and rotating a total of 1000 revolutions, the specimens were weighed before and after the test respectively, and the weight loss rate was calculated. The test results are shown in Table 1 below.

[0057] Table 1

[0058] As can be seen from the above table, the present application has a good wear resistance effect. From the electron micrographs of the fracture surfaces of Example 1 compared with those of Comparative Examples 1 - 4, it can be seen that the fracture surface of Example 1 has a greater roughness, indicating that the cross-linked structure is formed among the raw material components, making the fracture surface contain large lamellae.

[0059] The above content is only an example and illustration 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 for substitution, 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 fall within the protection scope of the present invention.

Claims

1. A method for preparing a highly wear-resistant carat tube, characterized in that: The specific steps include: Step A1: high-density polyethylene, acryloyl chloride and diisopropylbenzene peroxide are mixed and melted to react to obtain pretreated polyethylene, the pretreated polyethylene and n-hexane are mixed and stirred, triethylamine and maleimide are added, and the temperature is raised to react to obtain modified polyethylene; Step A2: mixing carboxymethyl cellulose, sodium hydroxide solution, furanyl chloride and dichloromethane, and adding hexadecyltrimethylammonium bromide to react to obtain pretreated cellulose; mixing the pretreated cellulose, p-aminophenylboronic acid, MES buffer, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide to react to obtain modified cellulose; Step A3: Weigh the following raw materials in parts by weight: 100-120 parts of modified polyethylene, 30-50 parts of modified resin, 20-30 parts of modified cellulose, 5-8 parts of cross-linking agent and 0.5-1 part of p-toluenesulfonic acid, heat and mix the raw materials, and then wind them together with the corrugated pipe reinforcement ribs coated with PP on a heated mold to form a pipe, thereby obtaining a high wear-resistant carat pipe.

2. The method for preparing a highly wear-resistant carat tube according to claim 1, characterized in that: The mass ratio of the high-density polyethylene, acryloyl chloride and diisopropylbenzene peroxide described in step A1 is 95:5:1, and the molar ratio of acyl chloride, triethylamine and maleimide on the pretreated polyethylene is 1:1.1:

1.

3. The method for preparing a highly wear-resistant carat tube according to claim 1, characterized in that: The amount ratio of carboxymethyl cellulose, sodium hydroxide solution, furanyl chloride, dichloromethane and hexadecyltrimethylammonium bromide described in step A2 is 1g:40mL:8g:40mL:6mmol, and the amount ratio of pretreated cellulose, p-aminophenylboronic acid, MES buffer, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide is 1g:5mol:100mL:5mol:5mol.

4. The method for preparing a highly wear-resistant carat tube according to claim 1, characterized in that: The modified resin is prepared by the following steps: Step B1: 4,4'-biphenol, toluene and glacial acetic acid are mixed evenly, stirred and concentrated nitric acid is added to react to obtain a modified monomer, and the modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, cyclopentane and toluene are mixed evenly, nitrogen is introduced for protection, and a reaction is carried out to obtain a modified polyetheretherketone; Step B2: uniformly mixing the modified polyetheretherketone, triethylamine and xylene, introducing nitrogen for protection, stirring and adding furanyl chloride to react to obtain pretreated polyetheretherketone; uniformly mixing the pretreated polyetheretherketone, palladium carbon catalyst, triethylamine and toluene, introducing hydrogen to react to obtain functionalized polyetheretherketone; Step B3: functionalized polyetheretherketone, 4-formylphenylboronic acid, 3A molecular sieve and xylene are mixed and reacted to obtain a modified resin.

5. The method for preparing a highly wear-resistant carat tube according to claim 4, characterized in that: The amount ratio of 4,4'-biphenol, toluene, glacial acetic acid and concentrated nitric acid in step B1 is 10mmol:10mL:12mL:1.5mL, and the amount ratio of modified monomer, 4,4'-difluorobenzophenone, bisphenol A, potassium carbonate, sodium carbonate, cyclopentane sulfone and toluene is 10mmol:30mmol:21mmol:20mmol:12mmol:35mL:10mL.

6. The method for preparing a highly wear-resistant carat tube according to claim 4, characterized in that: The molar ratio of the hydroxyl group, triethylamine and furanyl chloride on the modified polyetheretherketone described in step B2 is 1:1.2:1, and the amount ratio of the nitro group, palladium carbon catalyst, triethylamine and toluene on the pretreated polyetheretherketone is 10mmol:200mg:1mg:60mL.

7. The method for preparing a highly wear-resistant carat tube according to claim 4, characterized in that: The usage ratio of the amino group on the functionalized polyetheretherketone, 4-formylphenylboronic acid and 3A molecular sieve described in step B3 is 1 mol:1 mol:100 g.

8. The method for preparing a highly wear-resistant carat tube according to claim 1, characterized in that: The cross-linking agent is prepared by the following steps: Pentaerythritol tetrakis(3-mercaptopropionate), butene glycol, benzophenone and dimethyl sulfoxide are mixed and subjected to ultraviolet irradiation reaction to prepare a crosslinking agent.

9. The method for preparing a highly wear-resistant carat tube according to claim 8, characterized in that: The molar ratio of pentaerythritol tetrakis(3-mercaptopropionic acid) ester to butene glycol is 1:

4.

10. A highly wear-resistant carat tube, characterized in that: Prepared according to any one of claims 1 to 9.

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