Antibacterial HDPE hollow wall winding pipe

Abstract

The invention discloses a quaternary phosphonium salt antibacterial polymer, and belongs to the technical field of high polymer materials. The structural general formula is shown in the specification, wherein n is equal to 25-50; n1 is equal to 2-4; r1, R2 and R3 are C2-C6 straight-chain alkyl groups, and X is one of Cl, Br and I. A pre-grafting strategy is adopted, and a quaternary phosphonium salt antibacterial agent is chemically bonded to a polymer chain in advance, so that the compatibility with a polyethylene substrate material is enhanced, the dispersity of the antibacterial agent is improved, the possibility of precipitation of the antibacterial agent is reduced, and the antibacterial effect of the antibacterial agent can be continuously and effectively exerted; the situation that the antibacterial effect is weakened due to precipitation of the antibacterial agent is avoided. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an antibacterial HDPE hollow wall winding tube. Background Art

[0002] HDPE hollow wall winding pipe is a kind of pipe that uses high-density polyethylene (HDPE) as the main component material. Through advanced extrusion process, HDPE is melted and made into a continuous hollow square tube matrix. Then, using winding molding technology, these matrices are tightly wound and fixed in a specific spiral or parallel manner to form a pipe with a unique structural wall. Due to its unique manufacturing process and excellent physical properties, this pipe occupies an important position in municipal infrastructure construction and is widely used in various pipe network systems, including but not limited to urban water supply and drainage networks, farmland irrigation and drainage systems, low-pressure water pipelines, and flood control and drainage facilities.

[0003] However, in the process of using traditional drainage and sewage pipes, pollutants, microorganisms and pathogens carried in the water gradually deposit on the inner wall of the pipes. As time goes by, the effective flow area of ​​the pipes will gradually decrease, resulting in a decrease in water flow and a decrease in drainage and sewage efficiency. This not only increases the maintenance cost of the system, but may also have an adverse impact on the city's drainage capacity and environmental quality.

[0004] Quaternary ammonium salt antimicrobial agents and quaternary phosphonium salt antimicrobial agents are often used as antimicrobial agents in the preparation of polyethylene pipes. Compared with quaternary ammonium salt antimicrobial agents, quaternary phosphonium salt antimicrobial agents have more superior antimicrobial activity. However, there are significant compatibility issues between quaternary phosphonium salt small molecules and polyethylene matrix, resulting in poor stability and easy precipitation from the base material. This phenomenon not only weakens its antimicrobial efficacy, but also may pose a potential threat to environmental safety and human health.

[0005] In addition, glass fiber can improve the specific strength of HDPE hollow wall winding pipe, enhance its impact resistance and creep resistance, and make the pipe have excellent dimensional stability and low warping characteristics. These advantages make glass fiber reinforced materials an ideal choice for thin-walled and lightweight structural parts. However, the interface compatibility between glass fiber and high-density polyethylene (HDPE) material is poor, which easily leads to the precipitation of glass fiber, which in turn leads to the reduction of strength and stiffness of plastics, and even causes cracks and fractures in the pipe.

[0006] CN 112679827 A discloses an antibacterial polyethylene pipe and a preparation method thereof, wherein the antibacterial properties of the pipe are improved by using a nano antibacterial agent and an antibacterial synergist. However, the invention directly blends the quaternary phosphonium salt with high-density polyethylene, without considering the compatibility of the antibacterial agent with the polymer substrate, and the compatibility of the glass microspheres with the high-density polyethylene. Summary of the invention

[0007] In order to solve the above problems in the prior art, the purpose of the present invention is to provide a quaternary phosphonium salt antibacterial polymer.

[0008] Another object of the present invention is to provide an application of a quaternary phosphonium salt antibacterial polymer in the preparation of an antibacterial material.

[0009] Another object of the present invention is to provide a HDPE antibacterial hollow wall winding tube.

[0010] Another object of the present invention is to provide an application of a HDPE antibacterial hollow wall winding pipe in drainage and sewage treatment.

[0011] In order to achieve the above object, the present invention provides the following technical solutions:

[0012] A quaternary phosphonium salt antibacterial polymer, the general structural formula of which is as follows:

[0013]

[0014] Wherein, n=25-50; n1=2-4; R1, R2, R3 are C2-C6 straight chain alkyl groups, and X is one of Cl, Br, and I.

[0015] The present invention adopts a pre-grafting strategy to pre-chemically bond the quaternary phosphonium salt antibacterial agent to the polymer chain, and utilizes the good compatibility between polymer molecules to achieve directional, uniform and low-concentration dispersion of the antibacterial agent in the polyethylene substrate. This treatment method not only stabilizes the position of the antibacterial agent in the matrix, but also ensures that the antibacterial agent can continuously and effectively exert its antibacterial effect, avoiding the weakening of the antibacterial effect caused by the precipitation of the antibacterial agent.

[0016] Compared with quaternary ammonium salt antimicrobial agents, quaternary phosphonium salt antimicrobial agents have superior antimicrobial activity, mainly because compared with nitrogen atoms, phosphorus atoms have larger atomic radius and corresponding ionic radius, which enhances their polarization ability, that is, the ability to attract electron pairs. Therefore, phosphorus atoms are more likely to lose electrons in chemical reactions, which enhances the positive charge in quaternary phosphonium salt molecules. The enhanced positive charge promotes the electrostatic interaction between quaternary phosphonium salts and negatively charged bacterial cell walls, that is, the electrostatic adsorption effect. This strong interaction not only enhances the affinity of quaternary phosphonium salts for bacterial surfaces, but also promotes their ability to penetrate bacterial membrane structures, ultimately leading to more effective bacterial killing effects.

[0017] Specifically, R1, R2, and R3 are at least one of ethyl, butyl, and hexyl.

[0018] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0019] S1. an alcohol ether compound undergoes an esterification reaction with polyacrylic acid to obtain an intermediate product;

[0020] S2. The intermediate product undergoes a nucleophilic substitution reaction with a phosphine alkane to obtain the quaternary phosphonium salt antibacterial polymer;

[0021] The structural formula of the alcohol ether compound is as follows:

[0022]

[0023] Wherein, n1=2-4; X is one of Cl, Br, and I;

[0024] The structural formula of the phosphinoalkane is as follows:

[0025]

[0026] Among them, R1, R2, and R3 are C2-C6 straight-chain alkyl groups.

[0027] Specifically, the polymerization degree of the polyacrylic acid is 25-50.

[0028] Specifically, the alcohol ether compound is at least one of triethylene glycol monochlorohydrin, 2-chloroethoxyethanol, 2-[2-[2-(2-chloroethoxy)ethoxy]ethoxy]ethanol, 2-(2-bromoethoxy)ethanol, brominated-diethylene glycol, brominated-tetraethylene glycol, 2-(2-iodoethoxy)ethanol, 2-(2-(2-iodoethoxy)ethoxy)ethane-1-ol, and 2-(2-(2-(2-iodoethoxy)ethoxy)ethoxy)ethane-1-ol.

[0029] Preferably, the alcohol ether compound is triethylene glycol monochlorohydrin.

[0030] The present invention adopts alcohol ether compounds as grafted small molecules, which can not only graft phosphine alkane onto polyacrylic acid, but also enhance the flexibility of plastics and reduce the precipitation of quaternary phosphonium salt antibacterial polymers. Moreover, such small molecules have low toxicity and can reduce harm to the environment.

[0031] Specifically, the phosphine alkane is at least one of triethylphosphine, tributylphosphine and trihexylphosphine.

[0032] Preferably, the phosphinoalkane is trihexylphosphine.

[0033] Specifically, the grafting rate of the intermediate product is 60 to 90%.

[0034] The invention controls the grafting rate of the quaternary phosphonium salt antibacterial polymer by controlling the added amount of the alcohol ether compound.

[0035] It should be noted that if the grafted ether bond side chain is too long and the steric hindrance is too large, the grafting rate will be reduced.

[0036] Specifically, the mass ratio of the polyacrylic acid, the alcohol ether compound and the phosphine alkane is 1:(2-7.5):(0.9-7.2).

[0037] Specifically, the esterification reaction time is 18 to 72 hours.

[0038] Specifically, the temperature of the esterification reaction is 20 to 30°C.

[0039] Specifically, the temperature of the nucleophilic substitution reaction is 75 to 85°C.

[0040] Specifically, the nucleophilic substitution reaction time is 18 to 48 hours.

[0041] Specifically, the catalyst for the nucleophilic substitution reaction is sodium iodide or sodium bicarbonate.

[0042] By controlling the mass ratio within the above range, the grafting rate of the alcohol ether compound can be increased.

[0043] The invention also protects the use of a quaternary phosphonium salt antibacterial polymer in the preparation of antibacterial materials.

[0044] A HDPE antibacterial composition comprises the following components in parts by weight: 100 parts of HDPE, 2-8 parts of quaternary phosphonium salt antibacterial polymer, 15-30 parts of polyethylene resin pre-impregnated long glass fiber reinforced impregnated particles, and 3-7 parts of masterbatch.

[0045] Specifically, the length of the long glass fiber reinforced impregnated particles is 10 to 25 mm.

[0046] Specifically, the preparation method of the long glass fiber reinforced impregnated pellets comprises the following steps:

[0047] The glass fiber, the compatibilizer and the HDPE are mixed, heated, shaped, cooled and cut into particles to obtain the long glass fiber reinforced impregnated particles.

[0048] The present invention pre-impregnates glass fibers with polyethylene resin to obtain long glass fiber reinforced impregnated particles, which significantly improves the dispersion uniformity of the long glass fibers in the polyethylene resin matrix, optimizes the spatial distribution of the long glass fibers in the matrix, and further enhances the interface compatibility between the long glass fibers and the polyethylene base material, thereby maximizing the reinforcing effect of the long glass fibers on the polyethylene composite material.

[0049] More specifically, the heating temperature is 220-240°C.

[0050] More specifically, the prepreg particles contain 55-65% glass fiber, 30-40% HDPE, and 1-10% maleic anhydride grafted polyethylene type compatibilizer.

[0051] A HDPE antibacterial hollow wall winding pipe comprises the HDPE antibacterial composition.

[0052] Specifically, the preparation method of the HDPE antibacterial hollow wall winding tube comprises the following steps:

[0053] The HDPE antibacterial composition is extruded and wound to obtain the HDPE antibacterial hollow wall winding tube.

[0054] It should be noted that in the HDPE pipe, the quaternary phosphonium salt antibacterial polymer is a low molecular weight flexible polymer relative to the HDPE base material, which can increase the toughness of the winding pipe, but reduce the rigidity of the winding pipe. In addition, the present invention improves the compatibility of glass fiber and HDPE and increases the ring stiffness of the winding pipe by adding long glass fiber reinforced impregnated particles to the HDPE pipe.

[0055] The melt flow rate of HDPE at 190°C and 2.16 kg is 0.23-0.45 g / 10 min. The determination method is in accordance with ASTM D1238 "Test method for measuring the melt flow rate of thermoplastics using an extrusion plastic meter".

[0056] More specifically, the extrusion temperature is 180°C to 210°C.

[0057] The present invention also protects the use of a HDPE antibacterial hollow wall winding pipe in drainage and sewage treatment.

[0058] Compared with the prior art, the present invention has the following technical effects:

[0059] The present invention adopts a pre-grafting strategy to chemically bond the quaternary phosphonium salt antibacterial agent to the polymer chain in advance, thereby enhancing the compatibility with the polyethylene base material, improving the dispersibility of the antibacterial agent, reducing the possibility of precipitation of the antibacterial agent, and ensuring that the antibacterial agent can continuously and effectively exert its antibacterial effect, thereby avoiding the weakening of the antibacterial effect caused by the precipitation of the antibacterial agent.

[0060] The invention improves the compatibility of glass fiber and polyethylene substrate by introducing long glass fiber impregnated particles, overcomes the insufficient ring rigidity of the current hollow wall winding tube and the reduced rigidity of the winding tube caused by the introduction of quaternary phosphonium salt antibacterial polymer. DETAILED DESCRIPTION

[0061] The technical scheme of the present invention is further illustrated by examples below. The examples are implemented under the premise of the technical scheme of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples. The experimental methods in the following examples, unless otherwise specified, are conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are purchased from conventional biochemical reagent stores.

[0062] E-type glass fiber: Manufacturer: Jushi Group Co., Ltd., Brand: EDR17-2400-362A;

[0063] HDPE: Manufacturer: Chevron Phillips Chemical, Brand: HHM5502BN, Melt flow rate: 0.35g / 10min (190℃ / 2.16kg);

[0064] Maleic anhydride grafted polyethylene type compatibilizer: Manufacturer: Coase, Brand: W1H.

[0065] The degree of polymerization of the polyacrylic acid used in the examples and comparative examples was 40.

[0066] Preparation method of glass fiber reinforced impregnated granules in the embodiments and comparative examples:

[0067] After mixing E-type glass fiber, maleic anhydride grafted polyethylene type compatibilizer and HDPE, the mixture is heated to 230°C and introduced into a long glass fiber impregnation mold. After cooling and cutting, the long glass fiber particles pre-impregnated with HDPE are 0.5 mm and 20 mm in length. The pre-impregnated particles contain 60% glass fiber, 35% HDPE and 5% maleic anhydride grafted polyethylene type compatibilizer.

[0068] Example 1

[0069] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0070] 100 g of polyacrylic acid was added to 1000 ml of dichloromethane, and 234 g of triethylene glycol monochlorohydrin was added. After esterification reaction at room temperature for 24 hours, the solvent was removed, and the crude product was dissolved in dichloromethane. After filtering, the solution was concentrated by rotary evaporation and precipitated in ether. After filtering, the product was dissolved in dichloromethane again, and the solvent was removed under vacuum conditions. The intermediate product was purified by methanol dialysis to obtain a grafting rate of 75%. The intermediate product was reacted with 92 g of triethylphosphine by nucleophilic substitution, and the reaction was carried out for 18 hours under the catalysis of sodium iodide at a reaction temperature of 80°C to generate a quaternary phosphonium salt antibacterial polymer-1. The product was dissolved in water and purified by dialysis, and the final yield was 65%.

[0071] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0072] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-1, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed, extruded by an extruder at an extrusion temperature of 200°C, and then wound to obtain a HDPE hollow wall winding tube.

[0073] Example 2

[0074] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0075] 100g of polyacrylic acid was added to 1000ml of N,N-dimethylformamide, and 468g of triethylene glycol monochlorohydrin was added. After esterification at room temperature for 48h, the solvent was removed by rotary evaporation, and the crude product was dissolved in dichloromethane. The filtered dichloromethane solution was concentrated by rotary evaporation and precipitated drop by drop in ether. After filtration, the product was recovered in dichloromethane again, and the solvent was removed under vacuum conditions. Finally, it was purified by methanol dialysis to obtain an intermediate product with a grafting rate of 85%; under the catalysis of NaHCO3, it reacted with 477g of tributylphosphine through nucleophilic substitution reaction for 48h, and the reaction temperature was 80°C to generate quaternary phosphonium salt antibacterial polymer-2. The product was dissolved in water and then dialyzed for purification, with a final yield of 65%.

[0076] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0077] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-2, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed, extruded by an extruder at an extrusion temperature of 195°C, and then wound to obtain a HDPE hollow wall winding tube.

[0078] Example 3

[0079] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0080] 100g of polyacrylic acid was added to 1000ml of dichloromethane, and 702g of triethylene glycol monochlorohydrin was added. After esterification reaction at room temperature for 72h, the solvent was removed by rotary evaporation, and the crude product was dissolved in dichloromethane. After filtering, the solution was obtained, and the solution was slowly precipitated in ether after concentration. The product was filtered and dissolved in dichloromethane again, and the solvent was removed by rotary evaporation. Finally, it was purified by methanol dialysis to obtain an intermediate product with a grafting rate of 90%. The intermediate product was reacted with 714g of trihexylphosphine by nucleophilic substitution for 48h at a reaction temperature of 80°C to generate a quaternary phosphonium salt antibacterial polymer-3. The product was dissolved in water and purified by dialysis, and the final yield was 77%.

[0081] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0082] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-3, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0083] Example 4

[0084] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0085] 100g of polyacrylic acid was added to 1000ml of dichloromethane, and 557g of 2-(2-(2-(2-chloroethoxy)ethoxy)ethoxy)ethanol was added. After esterification at room temperature for 18h, the solvent was removed, and the crude product was dissolved in dichloromethane. After filtering, the solution was concentrated by rotary evaporation and precipitated in ether. After filtering, the product was dissolved in dichloromethane again, and the solvent was removed under vacuum conditions. Finally, it was purified by methanol dialysis to obtain an intermediate product with a grafting rate of 60%. The intermediate product was reacted with 476g of trihexylphosphine by nucleophilic substitution for 48h at a reaction temperature of 80°C to generate a quaternary phosphonium salt antibacterial polymer-4. The product was dissolved in water and purified by dialysis with a final yield of 52%.

[0086] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0087] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-4, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0088] Example 5

[0089] A method for preparing a quaternary phosphonium salt antibacterial polymer comprises the following steps:

[0090] 100g of polyacrylic acid was added to 1000ml of dichloromethane, and 568g of 2-(2-iodoethoxy)ethanol was added. After esterification reaction at room temperature for 18h, the solvent was removed by rotary evaporation, and the crude product was dissolved in dichloromethane. After filtering, the solution was concentrated by rotary evaporation and precipitated in ether. After filtering, a solid product was obtained. The product was dissolved in dichloromethane, the solvent was removed under vacuum conditions, and finally purified by methanol dialysis to obtain an intermediate product with a grafting rate of 80%; the intermediate product was reacted with 635g of trihexylphosphine by nucleophilic substitution for 48h at a reaction temperature of 80°C to generate a quaternary phosphonium salt antibacterial polymer-5. The product was dissolved in water and then dialyzed for purification with a final yield of 69%.

[0091] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0092] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-5, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0093] Example 6

[0094] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0095] 100 parts of HDPE resin powder, 2 parts of quaternary phosphonium salt antibacterial polymer-5, 30 parts of 20 mm long glass fiber reinforced impregnated particles, and 3 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0096] Example 7

[0097] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0098] 100 parts of HDPE resin powder, 8 parts of quaternary phosphonium salt antibacterial polymer-5, 15 parts of 20 mm long glass fiber reinforced impregnated particles, and 7 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0099] Comparative Example 1

[0100] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0101] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-3, 20 parts of 0.5 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 210°C, and then wound to obtain a HDPE hollow wall winding tube.

[0102] Comparative Example 2

[0103] A method for preparing a HDPE hollow wall winding pipe comprises the following steps:

[0104] 100 parts of HDPE resin powder, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 200°C, and then wound to obtain a HDPE hollow wall winding tube.

[0105] Comparative Example 3

[0106] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0107] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-3 and 5 parts of masterbatch were added and mixed, and then extruded by an extruder at an extrusion temperature of 195° C., and then wound to obtain a HDPE hollow wall winding tube.

[0108] Comparative Example 4

[0109] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0110] 100 parts of HDPE resin powder, 6 parts of quaternary phosphonium salt antibacterial polymer-3, 20 parts of 20 mm long unimpregnated glass fibers, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 200°C, and then wound to obtain a HDPE hollow wall winding tube.

[0111] Comparative Example 5

[0112] A method for preparing a HDPE antibacterial hollow wall winding tube comprises the following steps:

[0113] 100 parts of HDPE resin powder, 6 parts of tetramethylphosphine chloride, 20 parts of 20 mm long glass fiber reinforced impregnated particles, and 5 parts of masterbatch were mixed and extruded by an extruder at an extrusion temperature of 205°C, and then wound to obtain a HDPE hollow wall winding tube.

[0114] Test method:

[0115] The HDPE hollow wall winding pipes of the above embodiments and comparative examples were tested by the following performance testing method:

[0116] Ring stiffness: in accordance with GB / T 9647-2015 "Determination of Ring Stiffness of Thermoplastic Plastic Pipes";

[0117] Antibacterial performance: The test was conducted in accordance with GB / T 31402-2023 "Determination of antibacterial activity on the surface of plastics and other non-porous materials". The samples prepared in different embodiments and comparative examples were placed in a bacterial culture dish, 0.2 ml of bacterial liquid was dropped into the culture dish, and the culture dish was kept at a constant temperature and humidity to test the number of viable bacteria after 24 hours and 6 months.

[0118] The raw material compositions of Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1.

[0119] Table 1

[0120]

[0121]

[0122] The performance tests of the HDPE hollow wall winding pipes (DN / ID 200) prepared in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 2.

[0123] Table 2

[0124]

[0125] It can be seen from Table 2 that the number of viable bacteria in the HDPE hollow wall winding tubes prepared in all embodiments of the present invention is less than 11×10 6 cfu / ml, ring stiffness greater than 11, viable count after 6 months <12×10 6 cfu / ml and ring stiffness are both greater than 10. It can be seen from Examples 1 to 3 that the longer the alkyl chain length of the phosphine alkane used, the better the antibacterial effect. It can be seen from Example 3 and Comparative Example 2 that when there is no quaternary phosphonium salt antibacterial polymer in HDPE, the antibacterial performance of the winding pipe is poor, which shows that the introduction of quaternary phosphonium salt antibacterial polymer into the HDPE hollow winding pipe can improve the antibacterial performance of the winding pipe. It can be seen from Example 3 and Comparative Example 5 that since the quaternary phosphonium salt is not grafted onto the polymer through an ether bond chain in Comparative Example 5, the antibacterial performance is greatly weakened after 6 months, which may be caused by the precipitation of the quaternary phosphonium salt. Therefore, grafting the quaternary phosphonium salt onto the polymer through an ether bond chain can effectively improve the compatibility of the quaternary phosphonium salt with the polyethylene substrate and reduce the precipitation of the antibacterial agent.

[0126] It can be seen from Example 3, Comparative Example 1 and Comparative Example 3 that long glass fibers can effectively improve the ring stiffness of the winding tube, showing a more significant reinforcement effect. Compared with short glass fibers, since the number of ends of long glass fibers per unit volume of resin is less, the phenomenon of stress concentration can be effectively reduced and the initial formation of cracks can be reduced. Therefore, long glass fibers can significantly improve the ring stiffness of the winding tube. It can be seen from Example 3 and Comparative Example 4 that the ring stiffness of glass fibers that have not been impregnated with polyethylene resin is not as good as that of glass fibers that have been impregnated. And because the compatibility of glass fibers with polymer substrates is not good, some glass fibers may precipitate after 6 months, which leads to a significant reduction in ring stiffness. The compatibility between the impregnated glass fibers and the high-density polyethylene (HDPE) resin matrix is ​​significantly improved, thereby giving the material more excellent mechanical properties.

[0127] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A quaternary phosphonium salt antibacterial polymer, characterized in that: Its general structure is as follows: Wherein, n=25-50; n1=2-4; R1, R2, R3 are C2-C6 straight chain alkyl groups, and X is one of Cl, Br, and I.

2. The quaternary phosphonium salt antibacterial polymer according to claim 1, characterized in that: The R1, R2, and R3 are at least one of ethyl, butyl, and hexyl.

3. A method for preparing the quaternary phosphonium salt antibacterial polymer as claimed in claim 1 or 2, characterized in that: The following steps are involved: S1. an alcohol ether compound undergoes an esterification reaction with polyacrylic acid to obtain an intermediate product; S2. The intermediate product undergoes a nucleophilic reaction with a phosphine-substituted alkane to obtain the quaternary phosphonium salt antibacterial polymer; The structural formula of the alcohol ether compound is as follows: Wherein, n1=2-4; X is one of Cl, Br, and I; The structural formula of the phosphinoalkane is as follows: Among them, R1, R2, and R3 are C2-C6 straight-chain alkyl groups.

4. The preparation method according to claim 3, characterized in that: The alcohol ether compound is at least one of triethylene glycol monochlorohydrin, 2-chloroethoxyethanol, 2-[2-[2-(2-chloroethoxy)ethoxy]ethoxy]ethanol, 2-(2-bromoethoxy)ethanol, brominated-diethylene glycol, brominated-tetraethylene glycol, 2-(2-iodoethoxy)ethanol, 2-(2-(2-iodoethoxy)ethoxy)ethane-1-ol, and 2-(2-(2-(2-iodoethoxy)ethoxy)ethoxy)ethane-1-ol.

5. The preparation method according to claim 3, characterized in that: The phosphinoalkane is at least one of triethylphosphine, tributylphosphine and trihexylphosphine.

6. The preparation method according to claim 3, characterized in that: The mass ratio of the polyacrylic acid, the alcohol ether compound and the phosphine alkane is 1:(2-7.5):(0.9-7.2).

7. Use of the quaternary phosphonium salt antibacterial polymer as claimed in claim 1 or 2 in the preparation of antibacterial materials.

8. A HDPE antibacterial composition, characterized in that: The invention comprises the following components in parts by weight: 100 parts of HDPE, 2-8 parts of the quaternary phosphonium salt antibacterial polymer as claimed in claim 1 or 2, 15-30 parts of polyethylene resin pre-impregnated glass fiber reinforced impregnated particles, and 3-7 parts of masterbatch.

9. A HDPE antibacterial hollow wall winding tube, characterized in that: Comprising the HDPE antibacterial composition as claimed in claim 8.

10. Use of the HDPE antibacterial hollow wall winding pipe as claimed in claim 9 in drainage and sewage treatment.

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