Antistatic PE water supply pipe and preparation method thereof

Abstract

The invention discloses an antistatic PE water supply pipe and a preparation method thereof, and belongs to the technical field of plastic pipes. The copolymerized ionic liquid formed by polymerization has higher thermal stability, so that the thermal stability and the antistatic property of the PE water supply pipe are greatly improved, the gaseous silicon dioxide has plasticizing property, and the bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate can have a synergistic effect with the antioxidant and the antistatic agent, so that the antistatic property of the PE water supply pipe is improved. The antistatic property and the anti-aging property of the PE water supply pipe are greatly improved. According to the invention, the antistatic PE water supply pipe is prepared by taking 3-methyl-5-(2-methallyl) pyridine tetrafluoroborate and quaternary ammonium salt copolymerized ionic liquid as an antistatic agent and gaseous silicon dioxide loaded bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a toughening anti-ultraviolet filler; and the material has excellent antistatic, anti-ultraviolet aging and mechanical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of plastic pipes, and in particular relates to an antistatic PE water supply pipe and a preparation method thereof. Background Art

[0002] Polyethylene (PE) water pipes have become one of the most widely used plastic pipe varieties due to their low hydraulic friction coefficient, resistance to acid, alkali, salt and electrochemical corrosion, excellent impact resistance, energy saving and environmental protection, and long service life. PE material itself is a non-polar material with a surface resistance of up to 10 15 ~10 18 Ω / m 2 When water supply pipes transport liquids, static electricity generated by physical processes such as friction and separation is easy to accumulate on the surface of the pipe. The long-term accumulation of static electricity may lead to electrostatic discharge, posing a potential threat to the pipeline system and its surrounding environment.

[0003] In the prior art, there is an antistatic polyethylene masterbatch containing an organic ionic liquid, a preparation method and a pipe. The antistatic polyethylene masterbatch is obtained by mixing raw materials including the following components: polyethylene, a conductive filler and an organic ionic liquid; the organic ionic liquid is an organic liquid containing cations and anions. The present invention can improve the dispersibility of the conductive carrier in polyethylene, and at the same time, the ionic liquid has conductivity, which greatly reduces the percolation threshold of the system's conductivity. Moreover, due to the low viscosity of the ionic liquid, the flexibility of the system can be improved, just like a plasticizer. However, after research, it was found that in the existing preparation method of antistatic PE water supply pipes, in order to improve the antistatic properties of PE water supply pipes, a large amount of conductive fillers or a single-component ionic liquid is added, which will lead to technical problems such as reduced mechanical properties and anti-aging properties of the pipes. Summary of the invention

[0004] The purpose of the present invention is to provide an antistatic PE water supply pipe and a preparation method thereof, which is used to solve the technical problem in the prior art that the mechanical properties and anti-aging properties of the pipe are reduced by adding a large amount of conductive filler or a single-component ionic liquid.

[0005] In order to achieve the above-mentioned purpose, an antistatic PE water supply pipe and a preparation method thereof are provided in the present invention, which adopts the following technical scheme:

[0006] An antistatic PE water supply pipe is prepared from the following components in parts by weight:

[0007] 85-95 parts of polyethylene;

[0008] 1-2 parts of polymer antistatic agent;

[0009] 1-2 parts of lubricant;

[0010] 0.5 to 5 parts of toughening and anti-ultraviolet filler;

[0011] 1-2 parts of antioxidant;

[0012] Preferably, the antioxidant is any one of antioxidants 1010, 1098, and 168.

[0013] Preferably, the polymer antistatic agent is an ionic liquid copolymerized from 3-methyl-5-(2-methylpropenyl)pyridinium tetrafluoroborate and a quaternary ammonium salt.

[0014] Preferably, the lubricant is any one of paraffin and calcium stearate.

[0015] Preferably, the toughening and anti-ultraviolet filler is fumed silica loaded with bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0016] A method for preparing an antistatic PE water supply pipe comprises the following steps:

[0017] S1, ultrasonically mixing the toughened anti-ultraviolet filler and the polymer antistatic agent to obtain a conductive mixture;

[0018] S2, putting polyethylene, conductive mixture, antioxidant and lubricant into a high-speed mixer and stirring and blending;

[0019] S3, after being evenly mixed, adding the mixture into a twin-rod extruder for melt extrusion to obtain extruded particles;

[0020] S4, adding the extruded particles into a single screw extruder to extrude an unshaped pipe;

[0021] S5. Put the unshaped pipe into a water tank for cooling to obtain an antistatic PE water supply pipe.

[0022] The synthetic reaction principles involved in the preparation of polymer antistatic agents are as follows:

[0023]

[0024]

[0025] The preparation method of the polymer antistatic agent comprises the following steps:

[0026] S11, add 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate and ethyl acetate into a three-necked flask, and heat to 50-60° C. under a nitrogen atmosphere to react until the system becomes clear and transparent;

[0027] S12, add the quaternary ammonium salt into a three-necked flask, add the initiator after 1 to 2 hours, raise the temperature to 65 to 70°C after the reaction system is stable, and continue the reaction for 4 to 6 hours;

[0028] S13, after the reaction is completed, filter, wash and dry to obtain an antistatic agent.

[0029] Wherein, the synthetic route of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate is as follows:

[0030]

[0031] The synthesis method of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate comprises the following steps:

[0032] S21, 3-methyl-5-(2-methylpropenyl)pyridine, ethyl bromide and toluene are placed in a three-necked flask, and refluxed under a nitrogen atmosphere;

[0033] S22, after the reaction is completed, toluene is removed, and the product is recrystallized three times with ethyl acetate, and the product is filtered, crushed, vacuum dried, and then 3-methyl-5-(2-methylpropenyl)pyridinium bromide is collected;

[0034] S23, adding 3-methyl-5-(2-methylpropenyl)pyridinium bromide, deionized water and p-methoxyphenol into a three-necked flask and stirring until the system becomes clear and transparent;

[0035] S24, dissolving sodium tetrafluoroborate in deionized water at 30-50° C. to form a sodium tetrafluoroborate salt solution, and then adding the sodium tetrafluoroborate salt solution into a three-necked flask to react while continuously stirring;

[0036] S25. After the reaction is completed, wash with deionized water and dry to obtain 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate.

[0037] As a further improved solution of the present invention, a method for preparing a toughened anti-ultraviolet filler comprises the following steps:

[0038] S31, adding bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate to anhydrous ethanol and dispersing the mixture evenly to prepare an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate;

[0039] S32, weighing gaseous silicon dioxide and dispersing it in an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, magnetically stirring the mixture at room temperature, and after the stirring is completed, placing it in a vacuum drying oven and decompressing it to obtain a solution containing a toughened anti-ultraviolet filler;

[0040] S33, separating the toughened anti-ultraviolet filler from the solution by suction filtration, washing for multiple times and then vacuum drying to obtain the toughened anti-ultraviolet filler.

[0041] Preferably, in S11 to S12, the added amounts of 3-methyl-5-(2-methylpropenyl)pyridinium tetrafluoroborate, ethyl acetate, quaternary ammonium salt and initiator are in a molar ratio of 1:10-15:1:0.1-0.5.

[0042] Preferably, in S12, the quaternary ammonium salt is any one of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride, 3-(allyloxy)-2-hydroxypropyltrimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium chloride.

[0043] Preferably, in S12, the initiator is any one of azobisisobutyronitrile, azobisisoheptanenitrile and dibenzoyl peroxide.

[0044] Preferably, in S13, drying is performed at 90-100° C. for 12-24 hours.

[0045] Preferably, in S21, the usage ratio of 3-methyl-5-(2-methylpropenyl)pyridine, ethyl bromide and toluene is 0.1 mol:0.1 mol:50-100 mL, and the mixture is refluxed at 40-50° C. for 16-24 h.

[0046] Preferably, in S22, vacuum drying is performed at 40-50° C. for 4-6 hours.

[0047] Preferably, in S23 to S24, the usage ratio of 3-methyl-5-(2-methylpropenyl)pyridinium bromide, deionized water, p-methoxyphenol and sodium tetrafluoroborate is 1 mol: 1-1.5 L: 0.002-0.005 mol: 1 mol.

[0048] Preferably, in S24, the molar ratio of sodium tetrafluoroborate to deionized water is 0.1:250-300 mL, and the reaction is carried out at 25-40° C. for 24-36 hours.

[0049] Preferably, in S25, the temperature of the deionized water is 40-50°C, and the drying is carried out at 40-50°C for 6-12 hours.

[0050] Preferably, in S31 to S32, the molar ratio of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate to gaseous silicon dioxide is 0.03-0.05:0.2-0.5.

[0051] Preferably, in S31, the concentration of the anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is 15-18 g / 100 mL.

[0052] Preferably, in S32, magnetic stirring is performed at 25-35° C. for 12-18 hours and the pressure is reduced for 6-10 hours.

[0053] Preferably, in S33, anhydrous ethanol and deionized water are used for alternate washing, and vacuum drying is performed for 10 to 20 hours.

[0054] Preferably, in S1, ultrasound is performed at 25-35° C. for 10-30 min.

[0055] Preferably, in S2, the main engine speed is set to 250-350 r / min, and the high-speed mixer stirs for 5-10 min.

[0056] Preferably, in S3, the feeder speed is 100-150 r / min, the twin-screw extruder feed temperature is 170-190°C, and the extrusion temperature is 190-220°C.

[0057] Preferably, in S4, the feed temperature of the single screw extruder is 155-185°C, and the temperature of the die mouth is 210-230°C.

[0058] Preferably, in S5, the cooling water temperature of the water tank is 10-30° C., and the cooling time is 1-4 hours.

[0059] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0060] 1. Based on the components of existing PE water supply pipes, the present invention introduces 3-methyl-5-(2-methylpropylene) pyridinium tetrafluoroborate and quaternary ammonium salt copolymer ionic liquid as an antistatic agent and gaseous silica-loaded bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate as a toughening and anti-ultraviolet filler; compared with adding a large amount of conductive fillers or a single-component ionic liquid to ensure antistatic properties, the PE water supply pipe has excellent antistatic, anti-ultraviolet aging and mechanical properties.

[0061] 2. The present invention uses 3-methyl-5-(2-methylpropenyl)pyridinium tetrafluoroborate and quaternary ammonium salt copolymer ionic liquid as antistatic agent, which solves the technical problem that the mechanical and anti-aging properties of PE water supply pipes are damaged by adding a single pyridine antistatic agent or a quaternary ammonium salt antistatic agent. The copolymer ionic liquid formed by polymerization has higher thermal stability than a single type of ionic liquid, which greatly improves the thermal stability and antistatic effect of PE water supply pipes, and the amount of antistatic agent added has no obvious effect on the mechanical properties and anti-ultraviolet aging properties of PE water supply pipes.

[0062] 3. The present invention uses gaseous silica loaded bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate as a toughening and anti-ultraviolet filler to enhance the mechanical properties and anti-ultraviolet aging properties of PE water supply pipes. Gaseous silica has plasticizing properties and promotes the uniform distribution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and antistatic agents in PE water supply pipes. Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate has anti-ultraviolet aging properties and can synergize with antioxidants and antistatic agents to greatly improve the antistatic and anti-aging properties of PE water supply pipes.

[0063] 4. In the process of preparing PE water supply pipes, the toughened anti-UV filler and the antistatic agent are first ultrasonically mixed to make the antistatic agent and the toughened anti-UV filler evenly mixed. When the filler is evenly dispersed in the PE water supply pipe, the dispersion of the antistatic agent is also promoted, thereby reducing the precipitation of the antistatic agent in the PE water supply pipe. DETAILED DESCRIPTION

[0064] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0065] Example 1: An antistatic PE water supply pipe of this example is prepared from the following ingredients in parts by weight: 850g polyethylene, 20g polymer antistatic agent, 20g lubricant, 50g toughening anti-ultraviolet filler, and 10g antioxidant, wherein the lubricant is calcium stearate and the antioxidant is antioxidant 1010.

[0066] The preparation method of the antistatic PE water supply pipe comprises the following steps:

[0067] S1, ultrasonically treating the above-mentioned toughened anti-ultraviolet filler and polymer antistatic agent at 25° C. for 10 min to obtain a conductive mixture;

[0068] S2, put the above-mentioned polyethylene, conductive mixture, antioxidant, and lubricant into a high-speed mixer and stir and blend, set the main machine speed to 250r / min, and stir the high-speed mixer for 10min;

[0069] S3, after mixing evenly, add to a twin-screw extruder, the feeder speed is 100r / min, the feeding temperature of the twin-screw extruder is 170°C, the extrusion temperature is 190°C, and the extruded particles are obtained by melt extrusion;

[0070] S4, adding the extruded particles into a single screw extruder, wherein the feed temperature of the single screw extruder is 155° C., the temperature of the die mouth is 210° C., and extruding to obtain an unshaped pipe;

[0071] S5. Put the unshaped pipe into the water tank and set the cooling water temperature to 10°C and the cooling time to 1 hour. After cooling, an antistatic PE water supply pipe is obtained.

[0072] The preparation method of the polymer antistatic agent comprises the following steps:

[0073] S11, add 23.4 g of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate and 88.1 g of ethyl acetate into a three-necked flask, and heat to 50° C. under a nitrogen atmosphere to react until the system becomes clear and transparent;

[0074] S12, add 22.4 g of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride into a three-necked flask, and then add 1.6 g of azobisisobutyronitrile after 1 hour, raise the temperature to 65° C. after the reaction system is stable, and continue the reaction for 4 hours;

[0075] S13. After the reaction is completed, the mixture is filtered, washed, and dried at 90° C. for 12 h to obtain an antistatic agent.

[0076] The synthesis method of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate comprises the following steps:

[0077] S21, 14.7 g of 3-methyl-5-(2-methylpropenyl)pyridine, 10.9 g of ethyl bromide, and 50 mL of toluene were placed in a three-necked flask, and refluxed in a nitrogen atmosphere at 40° C. for 16 h;

[0078] S22, after the reaction is completed, toluene is removed, and the product is recrystallized three times with ethyl acetate, and the product is filtered and crushed, and vacuum dried at 40° C. for 4 h, and then 3-methyl-5-(2-methylpropenyl)pyridinium bromide is collected;

[0079] S23, add 25.6 g of 3-methyl-5-(2-methylpropenyl)pyridinium bromide, 100 mL of deionized water, and 0.03 g of p-methoxyphenol into a three-necked flask and stir until the system becomes clear and transparent;

[0080] S24, dissolving 11 g of sodium tetrafluoroborate in 250 mL of deionized water at 30° C. to form a sodium tetrafluoroborate salt solution, adding the sodium tetrafluoroborate salt solution into a three-necked flask and reacting at 25° C. for 24 h with continuous stirring;

[0081] S25. After the reaction is completed, wash with deionized water at 40°C and dry at 40-50°C for 6 hours to obtain 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate.

[0082] The preparation method of the toughened anti-ultraviolet filler comprises the following steps:

[0083] S31, 14.4g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate was added to anhydrous ethanol and dispersed uniformly to prepare a 15g / 100mL anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate;

[0084] S32, weighing 12 g of gaseous silicon dioxide and dispersing it in an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, magnetically stirring the mixture at room temperature for 12 h, and after the stirring, placing it in a vacuum drying oven under reduced pressure for 6 h to obtain a solution containing a toughened anti-ultraviolet filler;

[0085] S33, separating the toughened anti-ultraviolet filler from the solution by suction filtration, washing with anhydrous ethanol and deionized water alternately for multiple times, and vacuum drying for 10 hours to obtain the toughened anti-ultraviolet filler.

[0086] Example 2: An antistatic PE water supply pipe of this example is prepared from the following ingredients in parts by weight: 900g polyethylene, 15g polymer antistatic agent, 15g lubricant, 15g toughening anti-ultraviolet filler, and 15g antioxidant, wherein the lubricant is calcium stearate and the antioxidant is antioxidant 1010.

[0087] The preparation method of the antistatic PE water supply pipe comprises the following steps:

[0088] S1, ultrasonically treating the toughened anti-ultraviolet filler and the polymer antistatic agent at 30° C. for 20 min to obtain a conductive mixture;

[0089] S2. Put polyethylene, conductive mixture, antioxidant and lubricant into a high-speed mixer and stir and blend them. Set the main machine speed to 300 r / min and stir the high-speed mixer for 10 minutes.

[0090] S3, after mixing evenly, add to a twin-screw extruder, the feeder speed is 150r / min, the feeding temperature of the twin-screw extruder is 180°C, the extrusion temperature is 200°C, and the extrusion particles are obtained by melt extrusion;

[0091] S4, adding the extruded particles into a single screw extruder, wherein the feed temperature of the single screw extruder is 180° C., the temperature of the die mouth is 220° C., and extruding to obtain an unshaped pipe;

[0092] S5. Put the unshaped pipe into the water tank and set the cooling water temperature to 20°C and the cooling time to 2 hours. After cooling, the antistatic PE water supply pipe is obtained.

[0093] The preparation method of the polymer antistatic agent comprises the following steps:

[0094] S11, add 23.4 g of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate and 100 g of ethyl acetate into a three-necked flask, and then heat to 60° C. under a nitrogen atmosphere to react until the system becomes clear and transparent;

[0095] S12, add 22.4g of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride into a three-necked flask, and then add 2g of azobisisobutyronitrile after 1.5h, raise the temperature to 65°C after the reaction system is stable, and continue the reaction for 5h;

[0096] S13. After the reaction is completed, filter and wash, and dry at 100° C. for 12 h to obtain an antistatic agent.

[0097] The synthesis method of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate comprises the following steps:

[0098] S21, put 14.7 g of 3-methyl-5-(2-methylpropenyl)pyridine, 10.9 g of ethyl bromide, and 80 mL of toluene into a three-necked flask, and reflux for reaction at 45° C. in a nitrogen atmosphere for 20 h;

[0099] S22, after the reaction is completed, toluene is removed, and the product is recrystallized three times with ethyl acetate, and the product is filtered and crushed, and vacuum dried at 40°C for 4 hours, and then 3-methyl-5-(2-methylpropenyl)pyridinium bromide is collected;

[0100] S23, add 25.6 g of 3-methyl-5-(2-methylpropenyl)pyridinium bromide, 300 mL of deionized water, and 0.04 g of p-methoxyphenol into a three-necked flask and stir until the system becomes clear and transparent;

[0101] S24, dissolving 11 g of sodium tetrafluoroborate in 40° C. deionized water to form a sodium tetrafluoroborate salt solution, adding the sodium tetrafluoroborate salt solution into a three-necked flask and reacting at 30° C. for 30 h with continuous stirring;

[0102] S25. After the reaction is completed, wash with deionized water at 40°C and dry at 40-50°C for 6 hours to obtain 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate.

[0103] The preparation method of the toughened anti-ultraviolet filler comprises the following steps:

[0104] S31, adding 19.2 g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate to anhydrous ethanol and uniformly dispersing to prepare a 17 g / 100 mL bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate anhydrous ethanol solution;

[0105] S32, weighing 18 g of gaseous silicon dioxide and dispersing it in an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, stirring the mixture magnetically at room temperature for 18 h, and after stirring, placing it in a vacuum drying oven under reduced pressure for 8 h to obtain a solution containing a toughened anti-ultraviolet filler;

[0106] S33, separating the toughened anti-ultraviolet filler from the solution by suction filtration, washing with anhydrous ethanol and deionized water alternately for multiple times, and vacuum drying for 12 hours to obtain the toughened anti-ultraviolet filler.

[0107] Example 3: An antistatic PE water supply pipe of this example is prepared from the following ingredients in parts by weight: 950g polyethylene, 10g polymer antistatic agent, 10g lubricant, 5g toughening anti-ultraviolet filler, and 10g antioxidant, wherein the lubricant is calcium stearate and the antioxidant is antioxidant 1010.

[0108] The preparation method of the antistatic PE water supply pipe comprises the following steps:

[0109] S1, ultrasonically treating the above-mentioned toughened anti-ultraviolet filler and polymer antistatic agent at 35° C. for 30 min to obtain a conductive mixture;

[0110] S2. Put the above-mentioned polyethylene, conductive mixture, antioxidant and lubricant into a high-speed mixer and stir and blend them. Set the main machine speed to 350 r / min and stir the high-speed mixer for 10 min.

[0111] S3, after mixing evenly, add the mixture into a twin-screw extruder, the feeder speed is 150r / min, the feed temperature of the twin-screw extruder is 190°C, the extrusion temperature is 220°C, and the extrusion particles are obtained by melt extrusion;

[0112] S4, adding the extruded particles into a single screw extruder, wherein the feed temperature of the single screw extruder is 185° C., the temperature of the die mouth is 230° C., and extruding to obtain an unshaped pipe;

[0113] S5. Put the unshaped pipe into the water tank and set the cooling water temperature to 30°C and the cooling time to 4 hours. After cooling, the antistatic PE water supply pipe is obtained.

[0114] Wherein, the preparation method of the polymer antistatic agent comprises the following steps:

[0115] S11, add 23.4 g of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate and 120 g of ethyl acetate into a three-necked flask, and then heat to 60° C. under a nitrogen atmosphere to react until the system becomes clear and transparent;

[0116] S12, add 22.4 g of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride into a three-necked flask, and then add 0.05 g of azobisisobutyronitrile after 2 hours, and raise the temperature to 70° C. after the reaction system is stable, and continue the reaction for 6 hours;

[0117] S13, after the reaction is completed, filter and wash, and dry at 100° C. for 24 hours to obtain an antistatic agent.

[0118] The synthesis method of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate comprises the following steps:

[0119] S21, put 14.7 g of 3-methyl-5-(2-methylpropenyl)pyridine, 10.9 g of ethyl bromide, and 100 mL of toluene into a three-necked flask, and reflux for reaction at 50° C. under nitrogen atmosphere for 24 h;

[0120] S22, after the reaction is completed, toluene is removed, and the product is recrystallized three times with ethyl acetate, and the product is filtered and crushed, and vacuum dried at 40°C for 4 hours, and then 3-methyl-5-(2-methylpropenyl)pyridinium bromide is collected;

[0121] S23, add 25.6 g of 3-methyl-5-(2-methylpropenyl)pyridinium bromide, 300 mL of deionized water, and 0.04 g of p-methoxyphenol into a three-necked flask and stir until the system becomes clear and transparent;

[0122] S24, dissolving 11 g of sodium tetrafluoroborate in 300 mL of deionized water at 50° C. to form a sodium tetrafluoroborate salt solution, adding the sodium tetrafluoroborate salt solution into a three-necked flask and reacting at 40° C. for 36 h with continuous stirring;

[0123] S25. After the reaction is completed, wash with deionized water at 40°C and dry at 50°C for 12 hours to obtain 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate.

[0124] The preparation method of the toughened anti-ultraviolet filler comprises the following steps:

[0125] S31, adding 24.1g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate to anhydrous ethanol and uniformly dispersing to prepare 18g / 100mL of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate anhydrous ethanol solution;

[0126] S32, weighing 30 g of gaseous silicon dioxide and dispersing it in an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, stirring the mixture magnetically at room temperature for 18 h, and after stirring, placing it in a vacuum drying oven under reduced pressure for 10 h to obtain a solution containing a toughened anti-ultraviolet filler;

[0127] S33, separating the toughened anti-ultraviolet filler from the solution by suction filtration, washing the solution with anhydrous ethanol and deionized water alternately for multiple times, and vacuum drying the solution for 20 hours to obtain the toughened anti-ultraviolet filler.

[0128] Comparative Example 1: The difference between this comparative example and Example 1 is that the polymer antistatic agent is replaced by an ionic liquid antistatic agent containing only 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride.

[0129] Comparative Example 2: This comparative example differs from Example 1 in that the toughening anti-ultraviolet filler is replaced with carbon black.

[0130] Experimental example

[0131] The antistatic PE water supply pipes prepared in each embodiment and comparative example were tested for performance data using commercially available testing equipment, and the test results are shown in the following table:

[0132] Table 1

[0133]

[0134] UV resistance test

[0135] The antistatic PE water supply pipes prepared in the examples and comparative examples were placed in a fluorescent UV aging box and aged for 28 days. The aging conditions were an irradiance of 0.76 W / m 2 , 8h of light exposure at 60℃, 4h of condensation at 50℃, and 12h of cycle. After 7d, the tensile yield strength and nominal strain at break were tested. The test results are shown in the following table:

[0136] Table 2

[0137]

[0138] It can be seen from Table 1 that the volume resistance and surface resistance of Examples 1 to 3 are both 10 6 The results show that the antistatic PE water supply pipe prepared by the present invention has lower resistance than ordinary PE pipes. The tensile yield strengths of Examples 1 to 3 are all above 30 MPa, and the nominal strain at break is all above 220%, indicating that the antistatic PE water supply pipe prepared by the present invention has excellent mechanical properties and excellent antistatic properties. It further illustrates that the polymer antistatic agent prepared by the present invention and the toughened anti-ultraviolet filler have toughening, plasticizing and antistatic effects on PE water supply pipes when used in combination.

[0139] It can be seen from Table 1 that the volume resistivity and surface resistivity of Comparative Examples 1 to 2 are higher than those of the embodiments, and the tensile yield strength and nominal strain at break have a significant downward trend relative to those of the embodiments. The reason is that the antistatic agent in Comparative Example 1 is an ionic liquid containing only a single component of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride. Although the antistatic agent has a certain antistatic ability, a large amount of it will damage the mechanical properties of the PE water supply pipe; the filler in Comparative Example 2 is carbon black, and when a large amount of it is added, it is unevenly dispersed in the PE water supply pipe, resulting in the volume resistivity and surface resistivity of the PE water supply pipe being higher than those of the embodiments, and the mechanical properties being reduced.

[0140] It can be seen from Table 1 and Table 2 that compared with Comparative Examples 1 to 2, the decrease in tensile yield strength and nominal strain at break of Examples 1 to 3 after ultraviolet aging is smaller than that of the Comparative Examples, indicating that the antistatic PE water supply pipe prepared by the present invention has excellent resistance to ultraviolet aging.

[0141] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0142] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antistatic PE water supply pipe, characterized in that: It is prepared from the following ingredients in parts by weight: 85-95 parts of polyethylene; 1-2 parts of polymer antistatic agent; 1-2 parts of lubricant; 0.5 to 5 parts of toughening and anti-ultraviolet filler; 1-2 parts of antioxidant; The polymer antistatic agent is an ionic liquid copolymerized by 3-methyl-5-(2-methylpropylene) pyridinium tetrafluoroborate and quaternary ammonium salt, and the toughening anti-ultraviolet filler is gas phase silica loaded with bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

2. The antistatic PE water supply pipe according to claim 1, characterized in that: The lubricant is one or both of paraffin and calcium stearate, and the antioxidant is a combination of one or more of antioxidants 1010, 1098, and 168.

3. A method for preparing an antistatic PE water supply pipe, characterized in that: The steps include: S1, ultrasonically mixing the toughened anti-ultraviolet filler and the polymer antistatic agent to obtain a conductive mixture; S2, putting polyethylene, conductive mixture, antioxidant and lubricant into a high-speed mixer and stirring and blending; S3, after being evenly mixed, adding the mixture into a twin-rod extruder for melt extrusion to obtain extruded particles; S4, adding the extruded particles into a single screw extruder to extrude an unshaped pipe; S5. Put the unshaped pipe into a water tank for cooling to obtain an antistatic PE water supply pipe.

4. The method for preparing an antistatic PE water supply pipe according to claim 3, characterized in that: The preparation method of the polymer antistatic agent comprises the following steps: S11, add 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate and ethyl acetate into a three-necked flask, then heat to 50-60° C. under a nitrogen atmosphere, and react until the system becomes clear and transparent; S12, add the quaternary ammonium salt into a three-necked flask, add the initiator after 1 to 2 hours, raise the temperature to 65 to 70°C after the reaction system is stable, and continue the reaction for 4 to 6 hours; S13, after the reaction is completed, filtering, washing and drying to obtain the polymer antistatic agent.

5. The method for preparing an antistatic PE water supply pipe according to claim 4, characterized in that: The synthesis method of 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate comprises the following steps: S21, 3-methyl-5-(2-methylpropenyl)pyridine, ethyl bromide and toluene are placed in a three-necked flask, and refluxed under a nitrogen atmosphere; S22, after the reaction is completed, toluene is removed, and the product is recrystallized three times with ethyl acetate, filtered, crushed, and vacuum dried to collect 3-methyl-5-(2-methylpropenyl)pyridinium bromide; S23, adding 3-methyl-5-(2-methylpropenyl)pyridinium bromide, deionized water and p-methoxyphenol into a three-necked flask and stirring until the system becomes clear and transparent; S24, dissolving sodium tetrafluoroborate in deionized water at 30-50° C. to form a sodium tetrafluoroborate salt solution, adding the sodium tetrafluoroborate salt solution into a three-necked flask to react while continuously stirring; S25. After the reaction is completed, wash with deionized water and dry to obtain 3-methyl-5-(2-methylpropenyl)pyridine tetrafluoroborate.

6. The method for preparing an antistatic PE water supply pipe according to claim 5, characterized in that: In S21, the dosage ratio of 3-methyl-5-(2-methylpropenyl)pyridine, ethyl bromide and toluene is 0.1 mol: 0.1 mol: 50-100 mL, and the reaction is refluxed at 40-50° C. for 16-24 h; in S22, the reaction is vacuum dried at 40-50° C. for 4-6 h; in S23 to S24, the dosage ratio of 3-methyl-5-(2-methylpropenyl)pyridine bromide, deionized water, p-methoxyphenol and sodium tetrafluoroborate is 1 mol: 1-1.5 L: 0.002-0.005 mol: 1 mol; in S24, the molar ratio of sodium tetrafluoroborate and deionized water is 0.1: 250-300 mL, and the reaction is carried out at 25-40° C. for 24-36 h; in S25, the temperature of deionized water is 40-50° C., and the reaction is carried out at 40-50° C. for 6-12 h.

7. The method for preparing an antistatic PE water supply pipe according to claim 4, characterized in that: In S11 to S12, the added amounts of 3-methyl-5-(2-methylpropenyl)pyridinium tetrafluoroborate, ethyl acetate, quaternary ammonium salt and initiator are in a molar ratio of 1:10-15:1:0.1-0.5; in S12, the quaternary ammonium salt is a combination of one or more of 3-(acryloyloxy)-2-hydroxypropyltrimethylammonium chloride, 3-(allyloxy)-2-hydroxypropyltrimethylammonium chloride, and (3-acrylamidopropyl)trimethylammonium chloride, and the initiator is a combination of one or more of azobisisobutyronitrile, azobisisoheptanenitrile, and dibenzoyl peroxide; in S13, drying is performed at 90-100°C for 12-24 hours.

8. The method for preparing an antistatic PE water supply pipe according to claim 3, characterized in that: The preparation method of the toughened anti-ultraviolet filler comprises the following steps: S31, adding bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate to anhydrous ethanol and dispersing the mixture evenly to prepare an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; S32, weighing gaseous silicon dioxide and dispersing it in an anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, magnetically stirring the mixture at room temperature, and after the stirring is completed, placing it in a vacuum drying oven and decompressing it to obtain a solution containing a toughened anti-ultraviolet filler; S33, separating the toughened anti-ultraviolet filler from the solution by suction filtration, washing multiple times and then vacuum drying to obtain the toughened anti-ultraviolet filler.

9. The method for preparing an antistatic PE water supply pipe according to claim 8, characterized in that: In S31 to S32, the molar ratio of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate and gaseous silica is 0.03-0.05:0.2-0.5; in S31, the concentration of the anhydrous ethanol solution of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is 15-18 g / 100 mL; in S32, magnetic stirring is performed at 25-35° C. for 12-18 h, and the pressure is reduced for 6-10 h; in S33, anhydrous ethanol and deionized water are used for alternate washing, and vacuum drying is performed for 10-20 h.

10. The method for preparing an antistatic PE water supply pipe according to claim 3, characterized in that: In the S1, ultrasound is applied at 25-35°C for 10-30 min; in the S2, the main engine speed is set to 250-350 r / min, and the high-speed mixer is stirred for 5-10 min; in the S3, the feeder speed is 100-150 r / min, the twin-screw extruder feed temperature is 170-190°C, and the extrusion temperature is 190-220°C; in the S4, the single-screw extruder feed temperature is 155-185°C, and the die mouth temperature is 210-230°C; in the S5, the water tank cooling water temperature is 10-30°C, and the cooling time is 1-4 h.

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