Preparation method of self-repairing modified polyolefin hose material for water supply pipe

Abstract

The invention relates to the technical field of polyolefin, and discloses a preparation method of a self-repairing modified polyolefin hose material for a water supply pipe, the preparation method comprises the following steps: taking mercaptoethylamine, acrylic acid, chloropropene and the like as raw materials, carrying out a series of reactions to prepare an intermediate product 2, carrying out two times of reaction on the intermediate product 2 and nano-zinc oxide, 4-amino-2, 2, 6, 7, 8-tetramethyl-1, 3, 4-tetramethyl-1, 3, 4-tetramethyl-1, 3, 4-tetramethyl-1, 3, 4-tetramethyl-1, 3-tetramethyl-1, 3- The self-repairing modified polyolefin hose material for the water supply pipe is obtained by reacting nano-zinc oxide-based gemini quaternary ammonium salt and hindered amine modified gemini quaternary ammonium salt with 2, 2, 6, 6-tetramethylpiperidine, introducing the nano-zinc oxide-based gemini quaternary ammonium salt and hindered amine modified gemini quaternary ammonium salt into polypropylene and polyethylene, uniformly mixing, melting and blending, extruding and granulating, and carrying out injection molding. The prepared modified polyolefin hose material has excellent self-repairing performance, antibacterial performance, anti-aging performance and mechanical performance, and the service life of a water supply pipe can be prolonged when the modified polyolefin hose material is applied to the water supply pipe.

Description

Technical Field

[0001] The present invention relates to the technical field of polyolefins, in particular to a method for preparing a self-repairing modified polyolefin hose material for a water supply pipe. Background Art

[0002] During use, the hose material used for water supply pipes is easily subject to friction or scratches, and will age, discolor, and become brittle under the influence of ultraviolet rays and temperature, losing its mechanical properties, which seriously affects the service life of the hose material.

[0003] Polyethylene is a thermoplastic resin produced through the polymerization of ethylene monomers. It exhibits excellent chemical stability and toughness, and is widely used in pipes, packaging materials, films, and other fields. Polypropylene is a thermoplastic polymer produced through the addition polymerization of propylene monomers. It exhibits properties such as wear resistance and heat resistance, and is widely used in clothing, films, pipes, and other fields.

[0004] For example, patent application publication number CN 112920492 A discloses a self-healing high-density polyethylene resin and its preparation method. Using polyethylene resin, disulfide compounds, and polyethylene wax as raw materials, the resulting material exhibits excellent self-healing and chemical resistance. However, hoses made with this high-density polyethylene resin are prone to mold, brittleness, and discoloration, impacting their service life and water safety.

[0005] Therefore, the present invention provides a method for preparing a self-repairing modified polyolefin hose material for a water supply pipe. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the present invention provides a method for preparing a self-repairing modified polyolefin hose material for water supply pipes. The prepared modified polyolefin hose material has excellent self-repairing efficiency, antibacterial properties, anti-aging properties and mechanical properties.

[0007] To achieve the above-mentioned purpose, the present invention provides the following technical solutions:

[0008] A method for preparing a self-repairing modified polyolefin hose material for a water supply pipe, the method comprising the following steps:

[0009] A1, nano zinc oxide is ultrasonically dispersed in propyl alcohol, intermediate product 2 is added thereto, at 80-90 ℃, reaction 10-14h, after finishing the reaction, centrifugation, deionized water washing, drying, gained is recorded as nano zinc oxide based gemini quaternary ammonium salt, wherein, the mass ratio of nano zinc oxide and intermediate product 2 is 1:15-20, in this reaction, nano zinc oxide is owing to having larger surface area and surface energy, therefore easily reunited, poor compatibility, utilize the hydroxyl contained in the nano zinc oxide surface and the carboxyl contained in the intermediate product 2 to carry out esterification in this reaction, reduce degree of agglomeration, introduce nano zinc oxide in the material, increase the compatibility of material and nano zinc oxide, obtain nano zinc oxide based gemini quaternary ammonium salt, its reaction scheme is:

[0010] ,in, It is nano zinc oxide;

[0011] A2, by 4-amino-2,2,6,6-tetramethyl piperidine, triethylamine are joined in DMF solvent, dispersion with stirring, then add intermediate product 2 wherein, at room temperature, reaction 2-4h, after reaction finishes, suction filtration, deionized water washing, drying, centrifugal, gained is recorded as hindered amine modified gemini quaternary ammonium salt, wherein, 4-amino-2,2,6,6-tetramethyl piperidine, triethylamine, the mass ratio of intermediate product 2 is 1-1.2:0.6-0.8:1, in this reaction, utilize 4-amino-2,2,6, the carboxyl contained in the amino contained in the 6-tetramethyl piperidine and the intermediate product 2 under the catalysis of triethylamine, carry out amidation reaction, obtain hindered amine modified gemini quaternary ammonium salt, namely introduce hindered amine structure in product, its reaction scheme is:

[0012] ;

[0013] A3. Dicumyl peroxide, nano zinc oxide-based gemini quaternary ammonium salt, and hindered amine-modified gemini quaternary ammonium salt are added to a mixture of polyethylene and polypropylene and mixed evenly, melt-blended in a twin-screw melt extruder, extruded into granules, and injection-molded in an injection molding machine. The obtained material is recorded as a self-repairing modified polyolefin hose material for water supply pipes. The present invention utilizes the diene structure contained in nano zinc oxide-based gemini quaternary ammonium salt and hindered amine-modified gemini quaternary ammonium salt, which is grafted and introduced into the polyolefin material to produce more chemical crosslinking sites. The branched structure contained therein can also increase the utilization and increase the crosslinking degree of the material, hinder the movement of the molecular chain, and increase the mechanical properties. The nano zinc oxide as an inorganic particle is uniformly dispersed in the material. When impacted, it can serve as a stress concentration point, consume energy, and induce a large number of silver streaks or shear bands, forming an organic-inorganic synergistic system for improving the mechanical properties of the material.

[0014] Preferably, in A3, the mass ratio of dicumyl peroxide, nano zinc oxide-based gemini quaternary ammonium salt, hindered amine-modified gemini quaternary ammonium salt, polyethylene, and polypropylene is 0.05-0.1:1-5:1-5:100:80-100.

[0015] Preferably, the preparation method of the intermediate product 2 comprises the following steps:

[0016] AA1. Under a nitrogen atmosphere, add mercaptoethylamine to a 30-40% by mass hydrogen peroxide solution, raise the temperature to 45-55°C, and stir to react for 5-8 hours. After the reaction, add ethyl acetate and continue the reaction for 1-2 hours. After the reaction, separate the liquids, take the supernatant, dry it, filter it under reduced pressure, and distill it. The result is recorded as bis(2-aminoethyl) disulfide. In this reaction, mercaptoethylamine is oxidized with hydrogen peroxide to obtain bis(2-aminoethyl) disulfide, i.e., a self-repairing dynamic disulfide bond is introduced into the product. The reaction route is as follows;

[0017] ;

[0018] AA2. Under a nitrogen atmosphere, bis(2-aminoethyl) disulfide and acrylic acid were added to a chloroform solvent. The reaction temperature was controlled at 45-55°C and the reaction was carried out for 20-26 hours. After the reaction, the product was washed with deionized water, distilled under reduced pressure, and dried. The obtained product was recorded as intermediate product 1. The mass ratio of bis(2-aminoethyl) disulfide to acrylic acid was 1:1.8-2.2. The diamino group contained in bis(2-aminoethyl) disulfide and the alkenyl group contained in acrylic acid were subjected to Michael addition reaction to introduce a carboxyl structure into the product to obtain intermediate product 1. The reaction scheme is as follows:

[0019] ;

[0020] AA3. Add the intermediate product 1 to deionized water, add a polymerization inhibitor and allyl chloride thereto, control the reaction temperature to 40-50°C, use 10g / L sodium hydroxide solution to adjust the pH to 7-8, and keep the reaction for 6-10h. After the reaction is completed, rotary evaporation, suction filtration, methanol washing, and drying are performed. The obtained product is recorded as intermediate product 2, wherein the mass ratio of intermediate product 1 to allyl chloride is 1:0.35-0.4. In this reaction, the tertiary amine contained in the intermediate product 1 is subjected to a quaternization reaction with allyl chloride, and a quaternary ammonium salt antibacterial structure is introduced into the product to obtain intermediate product 2. The reaction route is:

[0021] .

[0022] Further preferably, in the AA3, the polymerization inhibitor is hydroquinone, the mass of which is 0.2-0.4% of the mass of the intermediate product 1, and its function is to prevent self-polymerization and increase the olefin content.

[0023] The beneficial effects of the present invention are:

[0024] The polyolefin hose material prepared by the present invention contains dynamically reversible disulfide bonds and hydrogen bonds. Disulfide bonds are a type of dynamically reversible weak covalent bond that can achieve a reversible exchange reaction between disulfide bonds or disulfide bonds and thiol groups. When introduced into the polyolefin hose material, the polyolefin hose material undergoes self-repair at room temperature or under certain conditions, thereby improving the self-repair efficiency of the polyolefin hose material. The material prepared by the present invention contains a large number of polar groups that can form a large number of hydrogen bonds. The hydrogen bonds contained therein are utilized to enhance the self-repair performance of the polyolefin hose material through bond breaking and formation.

[0025] The polyolefin hose material prepared by the present invention contains photocatalytic antibacterial nano-zinc oxide and a gemini quaternary ammonium salt structure. Leveraging the antibacterial properties of both, their introduction into the polyolefin hose material can enhance the material's antibacterial properties. The modified polyolefin hose material prepared by the present invention exhibits excellent self-repairing, antibacterial, anti-aging, and mechanical properties, and its application in water supply pipes can extend the service life of the pipes. DETAILED DESCRIPTION

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the specific implementation methods of the present invention will be described below. Obviously, the embodiments described below are only some embodiments of the present invention. For those skilled in the art, other implementation methods can be obtained based on these embodiments without inventive work.

[0027] Example 1

[0028] A1. Under a nitrogen atmosphere, add 20 g of mercaptoethylamine to a 30% by mass hydrogen peroxide solution, heat to 50°C, and stir to react for 8 h. After the reaction, add 50 mL of ethyl acetate and continue the reaction for 1 h. After the reaction, separate the liquids, take the supernatant, dry it, filter it under reduced pressure, and distill it. The resulting product is recorded as bis(2-aminoethyl) disulfide.

[0029] A2. Under a nitrogen atmosphere, 10 g of bis(2-aminoethyl) disulfide and 18 g of acrylic acid were added to a chloroform solvent. The reaction temperature was controlled at 55°C and the reaction was carried out for 24 h. After the reaction, the mixture was washed with deionized water, distilled under reduced pressure, and dried. The obtained product was recorded as intermediate 1.

[0030] A3. Add 10 g of intermediate product 1 to deionized water, then add 0.03 g of hydroquinone inhibitor and 3.5 g of allyl chloride, control the reaction temperature to 45 ° C, use 10 g / L sodium hydroxide solution to adjust the pH to 7, keep the reaction warm for 10 hours, after the reaction is completed, rotary evaporation, suction filtration, methanol washing, and drying. The result is recorded as intermediate product 2.

[0031] A4. Ultrasonic dispersion of 0.5 g of nano zinc oxide in propanol was added thereto, and 7.5 g of intermediate product 2 was reacted at 85° C. for 10 h. After the reaction was completed, the mixture was centrifuged, washed with deionized water, and dried. The obtained product was recorded as nano zinc oxide-based gemini quaternary ammonium salt.

[0032] A5. Add 5 g of 4-amino-2,2,6,6-tetramethylpiperidine and 3 g of triethylamine to N,N-dimethylformamide solvent, stir and disperse, then add 5 g of intermediate product 2 thereto, react at room temperature for 4 h. After the reaction is completed, filter, wash with deionized water, dry, and centrifuge. The obtained product is recorded as hindered amine-modified gemini quaternary ammonium salt.

[0033] A6. Add 0.05 g of dicumyl peroxide, 1 g of nano zinc oxide-based gemini quaternary ammonium salt, and 1 g of hindered amine-modified gemini quaternary ammonium salt to a mixture of 100 g of polyethylene and 100 g of polypropylene, mix evenly, melt blend in a twin-screw melt extruder, extrusion granulate, the twin-screw extruder temperature is 180° C., the speed is 200 r / min, and injection molding is performed in an injection molding machine at a temperature of 200° C. The obtained material is recorded as a self-repairing modified polyolefin hose material for water supply pipes; in this process, dicumyl peroxide is used as a peroxide cross-linking agent, and the peroxide decomposes at high temperature to generate free radicals. The free radicals attack the macromolecular chains, capture hydrogen atoms on the macromolecular chains, form macromolecular free radicals, and collide and couple with other free radicals to form a cross-linked network structure. The present invention utilizes nano zinc oxide-based gemini quaternary ammonium salts and hindered amine-modified gemini quaternary ammonium salts not only as additives but also utilizes the diene structure contained therein as a crosslinking aid. The free radicals generated by the decomposition of dicumyl peroxide trigger the double bonds contained in the nano zinc oxide-based gemini quaternary ammonium salts and hindered amine-modified gemini quaternary ammonium salts to form active sites, which react with the active sites on the macromolecular chain to form chemical bonds, thereby crosslinking to form a chemical network structure. In addition, the material prepared by the present invention contains a large number of branched structures, which are crosslinked and entangled with the main chain structure to form a physical network structure, forming a chemical-physical network structure. When subjected to external stress, the stress exerted on the material can be dispersed along the network structure, thereby improving the mechanical properties of the material.

[0034] Example 2

[0035] A1. Under a nitrogen atmosphere, add 20 g of mercaptoethylamine to a 40% by mass hydrogen peroxide solution, raise the temperature to 55°C, and stir for 5 h. After the reaction, add 50 mL of ethyl acetate and continue the reaction for 2 h. After the reaction, separate the liquids, take the supernatant, dry it, filter it under reduced pressure, and distill it. The resulting product is recorded as bis(2-aminoethyl) disulfide.

[0036] A2. Under a nitrogen atmosphere, 10 g of bis(2-aminoethyl) disulfide and 20 g of acrylic acid were added to a chloroform solvent. The reaction temperature was controlled at 50°C and the reaction was carried out for 26 h. After the reaction, the mixture was washed with deionized water, distilled under reduced pressure, and dried. The obtained product was recorded as intermediate 1.

[0037] A3. Add 10 g of intermediate product 1 to deionized water, then add 0.02 g of hydroquinone inhibitor and 4 g of allyl chloride, control the reaction temperature to 50°C, adjust the pH to 8 with 10 g / L sodium hydroxide solution, and keep the reaction warm for 6 h. After the reaction is completed, evaporate the mixture, filter with suction, wash with methanol, and dry. The result is recorded as intermediate product 2.

[0038] A4. Ultrasonic dispersion of 0.5 g of nano zinc oxide in propanol was added with 9 g of intermediate product 2. The mixture was reacted at 90° C. for 12 h. After the reaction, the mixture was centrifuged, washed with deionized water, and dried. The obtained product was recorded as nano zinc oxide-based gemini quaternary ammonium salt.

[0039] A5. Add 6 g of 4-amino-2,2,6,6-tetramethylpiperidine and 4 g of triethylamine to N,N-dimethylformamide solvent, stir and disperse, then add 5 g of intermediate product 2 thereto, react at room temperature for 3 h. After the reaction is completed, filter, wash with deionized water, dry, and centrifuge. The obtained product is recorded as hindered amine-modified gemini quaternary ammonium salt.

[0040] A6. Add 0.08 g of dicumyl peroxide, 2 g of nano zinc oxide-based gemini quaternary ammonium salt, and 3 g of hindered amine-modified gemini quaternary ammonium salt to a mixture of 100 g of polyethylene and 90 g of polypropylene, mix evenly, melt blend in a twin-screw melt extruder, and extrusion granulate. The twin-screw extruder temperature is 180 ° C and the speed is 200 r / min. The product is injection molded in an injection molding machine at a temperature of 200 ° C. The obtained product is recorded as a self-repairing modified polyolefin hose material for water supply pipes.

[0041] Example 3

[0042] A1. Under a nitrogen atmosphere, add 20 g of mercaptoethylamine to a 30% by mass hydrogen peroxide solution, heat to 45°C, and stir to react for 8 h. After the reaction, add 50 mL of ethyl acetate and continue the reaction for 2 h. After the reaction, separate the liquids, take the supernatant, dry it, filter it under reduced pressure, and distill it. The resulting product is recorded as bis(2-aminoethyl) disulfide.

[0043] A2. Under a nitrogen atmosphere, 10 g of bis(2-aminoethyl) disulfide and 22 g of acrylic acid were added to a chloroform solvent. The reaction temperature was controlled at 45°C and the reaction was carried out for 20 h. After the reaction, the mixture was washed with deionized water, distilled under reduced pressure, and dried. The obtained product was recorded as intermediate 1.

[0044] A3. Add 10 g of intermediate product 1 to deionized water, then add 0.04 g of hydroquinone inhibitor and 3.5 g of allyl chloride, control the reaction temperature to 45 ° C, use 10 g / L sodium hydroxide solution to adjust the pH to 7, keep the reaction warm for 10 hours, after the reaction is completed, rotary evaporation, suction filtration, methanol washing, and drying. The result is recorded as intermediate product 2.

[0045] A4. Ultrasonic dispersion of 0.5 g of nano zinc oxide in propanol was added with 10 g of intermediate product 2. The mixture was reacted at 80° C. for 14 h. After the reaction, the mixture was centrifuged, washed with deionized water, and dried. The obtained product was recorded as nano zinc oxide-based gemini quaternary ammonium salt.

[0046] A5. Add 6 g of 4-amino-2,2,6,6-tetramethylpiperidine and 4 g of triethylamine to N,N-dimethylformamide solvent, stir and disperse, then add 5 g of intermediate product 2 thereto, react at room temperature for 2 h. After the reaction is completed, filter, wash with deionized water, dry, and centrifuge. The obtained product is recorded as hindered amine-modified gemini quaternary ammonium salt.

[0047] A6. 0.1 g of dicumyl peroxide, 3 g of nano zinc oxide-based gemini quaternary ammonium salt, and 5 g of hindered amine-modified gemini quaternary ammonium salt are added to a mixture of 100 g of polyethylene and 80 g of polypropylene and mixed evenly. The mixture is melt-blended in a twin-screw melt extruder, extruded and granulated, and the temperature of the twin-screw extruder is 180 ° C and the speed is 200 r / min. The product is injection molded in an injection molding machine at a temperature of 200 ° C. The obtained product is recorded as a self-repairing modified polyolefin hose material for water supply pipes; the nano zinc oxide-based gemini quaternary ammonium salt and hindered amine-modified gemini quaternary ammonium salt of the present invention contain uniformly dispersed nano zinc oxide and hindered amine structure to improve the anti-aging performance of the polyolefin hose material.

[0048] Comparative Example 1

[0049] The preparation method of a self-repairing polyolefin hose material for water supply pipes provided in this comparative example is roughly the same as that in Example 1, with the main difference being that this comparative example 1 does not contain nano zinc oxide-based gemini quaternary ammonium salt.

[0050] Comparative Example 2

[0051] The preparation method of a self-repairing polyolefin hose material for water supply pipes provided in this comparative example is substantially the same as that in Example 1, with the main difference being that this comparative example 1 does not contain hindered amine-modified gemini quaternary ammonium salt.

[0052] Comparative Example 3

[0053] The preparation method of a self-repairing polyolefin hose material for water supply pipes provided in this comparative example is roughly the same as that in Example 1, the main difference is that 1g of intermediate product 2 is used in this comparative example 1 instead of hindered amine-modified gemini quaternary ammonium salt and nano zinc oxide-based gemini quaternary ammonium salt.

[0054] With reference to GB / T16422.3-2014, a UV aging test was carried out at a temperature of 50°C, a relative humidity of 50%, and an aging time of 10 h.

[0055] Refer to GB / T1040.1-2018 to test the mechanical properties of materials.

[0056] Table 1

[0057]

[0058] As can be seen from the table, the polyolefin hose material prepared by the present invention has good mechanical properties and anti-ultraviolet aging properties. Comparative Example 1 contains hindered amine-modified gemini quaternary ammonium salt, Comparative Example 2 contains nano zinc oxide-based gemini quaternary ammonium salt, and Comparative Example 3 contains only intermediate product 2. Because Comparative Example 1 and Comparative Example 2 contain 4 hindered amine structures and uniformly dispersed nano zinc oxide structures, both of which are anti-ultraviolet structures, and there are no two structures in Comparative Example 3, the anti-ultraviolet properties of Comparative Example 1 and Comparative Example 2 are better than those of Comparative Example 3, and from Example 1 and Comparative Example 1 and Comparative Example 2, the anti-ultraviolet properties of the material containing both structures are better, and as the amount of the two structures increases, the anti-ultraviolet properties are more excellent. Therefore, the polyolefin hose material prepared by the present invention has excellent anti-ultraviolet aging properties.

[0059] At the same time, the nano zinc oxide-based gemini quaternary ammonium salt and hindered amine-modified gemini quaternary ammonium salt prepared by the present invention contain uniformly dispersed nano zinc oxide, branched structures and polar groups; the nano zinc oxide is uniformly dispersed in the material, and when subjected to external stress, it can consume energy by generating a large number of silver streaks or shear bands, thereby improving the mechanical properties of the material; the more branched structures contained therein can be cross-linked and entangled with each other to form a cross-linked network structure. When subjected to external stress, the stress can be dispersed into other molecular chains along the cross-linking sites, thereby improving the mechanical properties of the material; the large number of polar groups therein can form a large number of hydrogen bonds in the molecular chain branches by forming hydrogen bonds. When subjected to external stress, the hydrogen bonds can further improve the mechanical properties of the material by absorbing stress. Therefore, it is applied to water supply pipes to improve the service life of the material.

[0060] Refer to GMW14688-2012 to test the self-healing performance of the material. The scratch force selected for the test is 10N. The color difference before and 30 minutes after scratching is calculated. The smaller the color difference value, the closer the material surface is to its pre-scratching state after scratching, and the better the self-healing performance.

[0061] Table 2:

[0062]

[0063] As can be seen from the table, the polyolefin pipe prepared by the present invention has a good self-repairing effect. Both the embodiment and the comparative example contain self-repairing dynamic covalent bonds, disulfide bonds and hydrogen bonds, but the content of disulfide bonds and hydrogen bonds in the embodiment is higher, so the color difference value is smaller and the self-repairing performance is better. Therefore, the material prepared by the present invention has good application prospects in the field of hose self-repair.

[0064] Refer to GB / T31402-2015 to test the antibacterial rate, and the test bacteria is Escherichia coli ATCC8739.

[0065] Table 3:

[0066]

[0067] As can be seen from the table, the polyolefin hose material prepared by the present invention has excellent antibacterial properties. Comparative Example 1 contains only a quaternary ammonium salt antibacterial structure, and Comparative Example 2 contains antibacterial nano zinc oxide and a quaternary ammonium salt structure. Therefore, the antibacterial performance of Comparative Example 1 is inferior to that of Comparative Example 2. In the embodiments, as the amount of hindered amine-modified gemini quaternary ammonium salt and nano zinc oxide-based gemini quaternary ammonium salt increases, the antibacterial property increases, and the antibacterial rate can reach up to 99.9%.

[0068] Finally, it should be noted that the above embodiments are intended only to illustrate the technical solutions of the present invention and do not constitute a limitation of the present invention. Although the present invention has been illustrated in detail through the above embodiments, those skilled in the art may still make various changes in form and details based on the technical contents described in the Summary of the Invention and Examples without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A method for preparing a self-repairing modified polyolefin hose material for a water supply pipe, characterized in that: The preparation method comprises the following steps: A1. Ultrasonic dispersion of nano zinc oxide in propanol, adding intermediate 2 thereto, reacting at 80-90°C for 10-14 hours. After the reaction, centrifugation, washing with deionized water, and drying are performed. The obtained product is recorded as nano zinc oxide-based gemini quaternary ammonium salt; A2, 4-amino-2,2,6,6-tetramethylpiperidine and triethylamine were added to N,N-dimethylformamide solvent, stirred and dispersed, and then intermediate 2 was added thereto. The reaction was carried out at room temperature for 2-4 hours. After the reaction was completed, the mixture was filtered, washed with deionized water, dried, and centrifuged. The obtained mixture was recorded as hindered amine-modified gemini quaternary ammonium salt; A3. Dicumyl peroxide, nano zinc oxide-based gemini quaternary ammonium salt, and hindered amine-modified gemini quaternary ammonium salt are added to a mixture of polyethylene and polypropylene, mixed evenly, melt-blended, extruded into granules, and injection-molded. The obtained material is recorded as a self-repairing modified polyolefin hose material for water supply pipes.

2. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 1, characterized in that: In the A1, the mass ratio of nano zinc oxide to the intermediate product 2 is 1:15-20.

3. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 1, characterized in that: In the A2, the mass ratio of 4-amino-2,2,6,6-tetramethylpiperidine, triethylamine and intermediate product 2 is 1-1.2:0.6-0.8:

1.

4. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 1, characterized in that: In the A3, the mass ratio of dicumyl peroxide, nano zinc oxide-based gemini quaternary ammonium salt, hindered amine-modified gemini quaternary ammonium salt, polyethylene, and polypropylene is 0.05-0.1:1-5:1-5:100:80-100.

5. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 1, characterized in that: The preparation method of the intermediate product 2 comprises the following steps: AA1. Under a nitrogen atmosphere, add mercaptoethylamine to a 30-40% by mass hydrogen peroxide solution, heat to 45-55°C, and stir to react for 5-8 hours. After the reaction is complete, add ethyl acetate and continue the reaction for 1-2 hours. After the reaction is complete, separate the liquids, take the supernatant, dry it, filter it under reduced pressure, and distill it. The resulting product is recorded as bis(2-aminoethyl) disulfide; AA2. Under a nitrogen atmosphere, add bis(2-aminoethyl) disulfide and acrylic acid to chloroform solvent, control the reaction temperature to 45-55°C, and react for 20-26 hours. After the reaction, wash with deionized water, distill under reduced pressure, and dry. The obtained product is recorded as intermediate 1. AA3. Add intermediate product 1 to deionized water, then add polymerization inhibitor and propylene chloride, control the reaction temperature to 40-50°C, use 10 g / L sodium hydroxide solution to adjust the pH to 7-8, keep the reaction warm for 6-10 hours, and after the reaction is completed, rotary evaporate, filter, wash with methanol, and dry. The result is recorded as intermediate product 2.

6. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 5, characterized in that: In the AA2, the mass ratio of bis(2-aminoethyl) disulfide to acrylic acid is 1:1.8-2.

2.

7. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 5, characterized in that: In the AA3, the mass ratio of the intermediate product 1 to allyl chloride is 1:0.35-0.

4.

8. The method for preparing the self-repairing modified polyolefin hose material for water supply pipe according to claim 5, characterized in that: In the AA3, the polymerization inhibitor is hydroquinone, and its mass is 0.2-0.4% of the mass of the intermediate product 1.

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