High-strength porcelain core antibacterial pipe and preparation process thereof

Abstract

The present application relates to the technical field of pipe material, more particularly, it relates to a high-strength porcelain core antibacterial pipe material and a preparation process thereof.The high-strength porcelain core antibacterial pipe material comprises the following parts: an antibacterial inner pipe and a heat-resistant outer pipe, the antibacterial inner pipe is prepared from antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin, the antibacterial glass fiber and the silver-loaded mesoporous silica material cooperate with each other to produce a synergistic effect in the antibacterial inner pipe, so that the prepared high-strength porcelain core antibacterial pipe material has strong antibacterial performance and strong antibacterial durability; the heat-resistant outer pipe is prepared by mixing modified mullite fiber, polypropylene resin and other additives, the modified mullite fiber has the characteristics of high-temperature resistance, low thermal conductivity and flame retardation, so that the heat-resistant outer pipe of the high-strength porcelain core antibacterial pipe material has good flame retardation, heat insulation effect and thermal dimensional stability, the problem that the pipe material is easily deformed and damaged due to heat is avoided, and the service life of the pipe material is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pipe material, more particularly, it relates to a high-strength porcelain core antibacterial pipe material and a preparation process thereof. BACKGROUND

[0002] The porcelain core antibacterial pipe material is a pipe material with antibacterial function, the surface of the pipe material is attached with an antibacterial agent, which can effectively inhibit the breeding and reproduction of bacteria in the pipe, and can be widely applied in the fields of drinking water, chemical industry, medicine, food and the like.

[0003] The antibacterial agent used in the porcelain core antibacterial pipe material is mainly divided into inorganic antibacterial agent and organic antibacterial agent, the commonly used inorganic antibacterial agent is silver-based antibacterial agent, the antibacterial agent mainly loads nano-silver in the carrier through physical adsorption or chemical grafting method, and then attaches the loaded carrier to the inner wall of the pipe material, and achieves the sterilization effect through the slow release of Ag+; however, the carrier of nano-silver at present is mainly traditional inorganic carrier such as zeolite, zirconium phosphate and clay, and the combination mode is mainly ion exchange, and the stability is poor, which leads to the falling and elution of the loaded Ag+, and greatly limits the antibacterial effect and application range of the silver-based antibacterial agent in the porcelain core antibacterial pipe material; and the organic antibacterial agent mainly includes nitrogen-containing ionic compounds, quaternary ammonium salt antibacterial agents and guanidine antibacterial agents, the use of these organic antibacterial agents in the porcelain core antibacterial pipe material generally has problems such as easy elution and easy decomposition at high temperature, which affects the antibacterial durability of the organic antibacterial agent in the porcelain core antibacterial pipe material, and the antibacterial agent needs to be supplemented regularly or the new pipe material needs to be replaced.

[0004] In addition, the outer layer of the porcelain core pipe material sold on the market is usually made of polypropylene, although the polypropylene has many advantages such as light weight, corrosion resistance, long service life, easy installation and reliable connection, however, the polypropylene material has poor flame retardant performance, poor dimensional stability and high linear expansion coefficient, which leads to the easy deformation of the porcelain core pipe material under heat, and limits the application range and service life of the porcelain core pipe material. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a high-strength porcelain core antibacterial pipe material with strong antibacterial performance and strong antibacterial durability, and a preparation process for improving the flame retardant and heat insulation performance of the porcelain core antibacterial pipe material.

[0006] A high-strength porcelain core antibacterial pipe material, characterized in that it comprises the following parts: an antibacterial inner pipe and a heat-resistant outer pipe.

[0007] The raw material of the antibacterial inner pipe comprises: antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin, and the mixing mass ratio of the antibacterial glass fiber, the silver-loaded mesoporous silica material and the polypropylene resin is (1-3) :(1-3) :(45-50).

[0008] The raw material of the antibacterial glass fiber comprises pre-treated glass fiber and antibacterial treatment solution, wherein the mass ratio of the pre-treated glass fiber to the antibacterial treatment solution is (1-10):(30-70), and the pre-treated glass fiber is obtained by sequentially treating glass fiber with hydrogen peroxide and titanate coupling agent;

[0009] The raw material of the antibacterial treatment solution comprises 20-48 parts by weight of organosilicon quaternary ammonium salt, 4-15 parts by weight of tetraethyl orthosilicate, 50-70 parts by weight of anhydrous ethanol and 80-130 parts by weight of deionized water;

[0010] The raw material of the silver-loaded mesoporous silica material comprises 5-18 parts by weight of surface-aminoized mesoporous silica, 20-50 parts by weight of anhydrous ethanol and 20-50 parts by weight of a silver nitrate solution with a concentration of 0.5 mol / L, wherein the surface-aminoized mesoporous silica is obtained by modifying the mesoporous silica with silane coupling agent KH-550 after dissolving the mesoporous silica in anhydrous ethanol;

[0011] The raw material of the heat-resistant outer tube comprises polypropylene resin, modified mullite fiber, color masterbatch, compatibilizer, lubricant and antioxidant, wherein the mass ratio of the polypropylene resin, the modified mullite fiber, the color masterbatch, the compatibilizer, the lubricant and the antioxidant is (80-140):(20-40):(3-12):(3-8):(0.5-1.5):(0.5-1);

[0012] The raw material of the modified mullite fiber comprises pre-treated mullite fiber and 10% silane coupling agent KH-550 aqueous solution, and the solid-liquid mass ratio is (1-8):(20-50);

[0013] The raw material of the pre-treated mullite fiber comprises 30-40 parts by weight of mullite fiber, 60-120 parts by weight of acetone solution and 80-150 parts by weight of sodium hydroxide solution with a concentration of 1 mol / L.

[0014] Further, a preparation process of the high-strength ceramic-core antibacterial pipe material comprises the following steps:

[0015] S1: preparing the antibacterial glass fiber, mixing organosilicon quaternary ammonium salt, tetraethyl orthosilicate, anhydrous ethanol and deionized water to prepare an antibacterial treatment solution, sequentially pre-treating glass fiber with hydrogen peroxide and titanate coupling agent, soaking the pre-treated glass fiber in the antibacterial treatment solution, and then stirring, standing, high-temperature reaction, washing and drying to obtain the antibacterial glass fiber;

[0016] S2: Preparation of silver-loaded mesoporous silica material, after dissolving the mesoporous silica in anhydrous ethanol, drop the silane coupling agent KH-550, after stirring and refluxing, filtering, washing, the surface aminated mesoporous silica is obtained, after dissolving the surface aminated mesoporous silica in anhydrous ethanol, add silver nitrate solution, avoid light, seal and stir, after filtering, washing and drying, the silver-loaded mesoporous silica material is obtained;

[0017] S3: Preparation of modified mullite fiber, after putting the mullite fiber into acetone solution, ultrasonic dispersion, washing and drying, the dried mullite fiber is put into sodium hydroxide solution, after heating, washing and drying, the pretreated mullite fiber is obtained, the pretreated mullite fiber is put into silane coupling agent KH-550 aqueous solution, water bath heating reaction, after filtering, washing and drying, the modified mullite fiber is obtained;

[0018] S4: Pipe material granulation and preparation of high-strength ceramic core antibacterial pipe material, after mixing the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin in proportion, granulation is carried out to obtain antibacterial inner layer granules, after mixing the polypropylene resin, modified mullite fiber, color masterbatch, compatibility agent, lubricant and antioxidant in proportion, granulation is carried out to obtain heat-resistant outer layer granules, after extruding the antibacterial inner layer granules and heat-resistant outer layer granules to make pipes, the antibacterial inner pipe and heat-resistant outer pipe are obtained, after co-extrusion, shaping and sizing, cooling, traction and cutting, the high-strength ceramic core antibacterial pipe material is obtained.

[0019] Further, the organosilicon quaternary ammonium salt is 3-(trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride, 3-(trimethoxysilyl) propyl trimethyl ammonium chloride, 3-(triethoxysilyl) propyl dimethyl octadecyl ammonium chloride or 3-(trihydroxysilyl propyl) dimethyl octadecyl ammonium chloride.

[0020] Further, the preparation of antibacterial glass fiber in step S1 specifically includes the following steps:

[0021] S1.1: After mixing 20-48 parts by weight of organosilicon quaternary ammonium salt, 4-15 parts by weight of tetraethyl orthosilicate and 50-70 parts by weight of anhydrous ethanol, 80-130 parts by weight of deionized water is added, and the mixture is stirred and reacted at 25-35℃ for 2-4h to obtain an antibacterial treatment solution;

[0022] S1.2: The glass fiber is added to the hydrogen peroxide with a concentration of 0.1 mol / L, the solid-liquid mass ratio of the glass fiber to the hydrogen peroxide with a concentration of 0.1 mol / L is (1-7):(10-20), and stirring is performed at 60-85°C for 15-30 min. Then, the oxidized glass fiber is taken out, and the oxidized glass fiber is completely immersed in a titanate coupling agent for 40-80 min. After filtration, washing and drying, the pretreated glass fiber is obtained.

[0023] S1.3: The pretreated glass fiber is completely immersed in an antibacterial treatment solution, the mass ratio of the pretreated glass fiber to the antibacterial treatment is (1-10):(30-70), stirring is performed for 20-40 min, and then the solution is left to stand at room temperature for 30-60 min. Then, the treated glass fiber is taken out and placed in an oven at 100-120°C for grafting reaction for 1-2 h. After the reaction, the reacted glass fiber is taken out, washed with deionized water for 1-3 times, and then placed in an oven at 65-85°C for drying for 30-60 min. The antibacterial glass fiber is obtained.

[0024] Further, the length of the glass fiber is 50-100 μm, and the diameter is 10-30 μm.

[0025] Further, the step S2 of preparing the silver-loaded mesoporous silica material specifically includes the following steps.

[0026] S2.1: 12-21 parts by weight of the mesoporous silica is dissolved in 40-90 parts by weight of anhydrous ethanol, 15-24 parts by weight of the silane coupling agent KH-550 is added dropwise, and stirring is performed under reflux for 8-12 h to obtain a mixed solution. Then, the mixed solution is subjected to suction filtration and washing to obtain the surface-aminoized mesoporous silica.

[0027] S2.2: 5-18 parts by weight of the surface-aminoized mesoporous silica is dissolved in 20-50 parts by weight of anhydrous ethanol, and 20-50 parts by weight of a silver nitrate solution with a concentration of 0.5 mol / L is added. Stirring is performed in the dark and under sealing for 3-4 h. Then, the silver-loaded mesoporous silica material is obtained through suction filtration, washing with ethanol with a volume fraction of 70%, washing with deionized water and drying.

[0028] Further, the step S3 of preparing the modified mullite fiber specifically includes the following steps.

[0029] S3.1: 30-40 parts by weight of the mullite fiber is placed in 60-120 parts by weight of an acetone solution, and ultrasonic dispersion is performed for 1-2 h. After washing and drying, the dried mullite fiber is placed in 80-150 parts by weight of a sodium hydroxide solution with a concentration of 1 mol / L, and heating is performed at 70-80°C for 1-2 h. After washing and drying, the pretreated mullite fiber is obtained.

[0030] S3.2: Put the pretreated mullite fibers into a 10% mass fraction of silane coupling agent KH-550 aqueous solution, the solid-liquid mass ratio of the pretreated mullite fibers to the 10% mass fraction of silane coupling agent KH-550 aqueous solution is (1-8):(20-50), 50-65℃ water bath heating for 2-4h, after heating, filter, wash 2-5 times with deionized water, dry, to obtain modified mullite fibers.

[0031] Further, step S4 pipe granule processing and high-strength ceramic core antibacterial pipe preparation, specifically comprising the following steps:

[0032] S4.1: Mix the antibacterial glass fibers, silver-loaded mesoporous silica material and polypropylene resin according to the proportion, the mixing ratio of the antibacterial glass fibers, silver-loaded mesoporous silica material and polypropylene resin is (1-3):(1-3):(45-50), stir and mix with a high-speed mixer for 5-10min, then extrude and granulate by using a double-screw extruder, the extrusion temperature is 180-230℃, to obtain antibacterial inner layer granules;

[0033] S4.2: Mix the polypropylene resin, modified mullite fibers, color masterbatch, compatibilizer, lubricant and antioxidant according to the proportion, the mixing mass ratio of the polypropylene resin, modified mullite fibers, color masterbatch, compatibilizer, lubricant and antioxidant is (80-140):(20-40):(3-12):(3-8):(0.5-1.5):(0.5-1), stir and mix with a high-speed mixer for 5-10min, then extrude and granulate by using a double-screw extruder, the extrusion temperature is 200-230℃, to obtain heat-resistant outer layer granules;

[0034] S4.3: Put the antibacterial inner layer granules into a single-screw extruder for extrusion, to obtain an antibacterial inner tube;

[0035] S4.4: Put the heat-resistant outer layer granules into another single-screw extruder for extrusion, to obtain a heat-resistant outer tube;

[0036] S4.5: Put the antibacterial inner tube and the heat-resistant outer tube into a co-extrusion device for co-extrusion, place the extruded material in a molding die for molding, after shaping, cooling, pulling and cutting, to obtain a high-strength ceramic core antibacterial pipe.

[0037] Further, the compatibilizer is polypropylene grafted maleic anhydride, maleic acid dibutyl ester, acrylamide or glycidyl methacrylate, the lubricant is fatty acid amide, stearate or polyethylene wax, and the antioxidant is antioxidant DLTP, antioxidant 1010 or antioxidant 168.

[0038] Further, the single screw extruder in step S4.3 has an extrusion temperature of 180-240 DEG C and a rotating speed of 40-60 r / min, and the single screw extruder in step S4.4 has an extrusion temperature of 180-240 DEG C and a rotating speed of 60-90 r / min.

[0039] The present application has the following advantages:

[0040] 1、In the present application, by preparing the antibacterial glass fiber, the quaternary ammonium salt molecules are grafted to the surface of the glass fiber, so that the glass fiber after grafting modification has antibacterial performance on escherichia coli and staphylococcus aureus, and can maintain good antibacterial stability, and overcomes the problem of poor durability such as elution and decomposition of organic antibacterial agent directly applied to the pipe.

[0041] 2、In the present application, by loading silver ions on the surface of the amino-functionalized mesoporous silica, Ag+ can be uniformly and stably distributed on the surface of the mesoporous silica, which can improve the antibacterial durability while ensuring the antibacterial performance, and help to solve the problems of poor stability and poor antibacterial durability of traditional carriers for nano-silver.

[0042] 3、In the present application, the antibacterial inner layer granules are prepared by using the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin, and the antibacterial inner tube is prepared by using the antibacterial inner layer granules, wherein the antibacterial glass fiber and silver-loaded mesoporous silica material cooperate with each other in the antibacterial inner tube to produce a synergistic effect, so that the prepared high-strength ceramic core antibacterial pipe has high-efficiency and long-lasting antibacterial effect on escherichia coli and staphylococcus aureus.

[0043] 4、In the present application, the heat-resistant outer layer granules are prepared by mixing modified mullite fiber, polypropylene resin and other additives, and the heat-resistant outer tube is prepared by using the heat-resistant outer layer granules, wherein the modified mullite fiber has the characteristics of high temperature resistance, low thermal conductivity and flame retardancy, which can improve the flame retardancy, heat insulation effect and thermal dimensional stability of the high-strength ceramic core antibacterial pipe, reduce the influence of pipe deformation caused by heat on the normal use of the pipe, and thus improve the application range and service life of the high-strength ceramic core antibacterial pipe. DETAILED DESCRIPTION

[0044] In order to enable those skilled in the art to better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application.

[0045] Embodiment 1

[0046] A preparation process of a high-strength ceramic core antibacterial pipe, specifically comprising the following steps:

[0047] S1: preparation of antibacterial glass fiber,

[0048] S1.1: 48 parts by weight of 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, 15 parts by weight of ethyl orthosilicate and 70 parts by weight of anhydrous ethanol were stirred and mixed, then 130 parts by weight of deionized water was added, and stirred at 35°C for 4h to obtain an antibacterial treatment solution;

[0049] S1.2: The glass fiber was added to the hydrogen peroxide solution with a concentration of 0.1 mol / L, wherein the length of the glass fiber was 60 μm, the diameter was 20 μm, and the solid-liquid mass ratio of the glass fiber to the hydrogen peroxide solution with a concentration of 0.1 mol / L was 7:20, and stirred at 85°C for 30 min, then the oxidized glass fiber was taken out and completely immersed in the titanate coupling agent for 80 min, and after filtration, washing and drying, the pretreated glass fiber was obtained;

[0050] S1.3: The pretreated glass fiber was completely immersed in the antibacterial treatment solution, and the mass ratio of the pretreated glass fiber to the antibacterial treatment was 1:7, and after stirring for 40 min, it was placed at room temperature for 60 min, then the treated glass fiber was taken out and placed in an oven at 120°C for grafting reaction for 2h, after the reaction was completed, the reacted glass fiber was taken out, washed with deionized water for 3 times, and then placed in an oven at 85°C for drying for 60 min, to obtain the antibacterial glass fiber;

[0051] S2: Preparation of silver-loaded mesoporous silica material,

[0052] S2.1: 21 parts by weight of mesoporous silica was dissolved in 90 parts by weight of anhydrous ethanol, and 24 parts by weight of silane coupling agent KH-550 was added dropwise, and stirred and refluxed for 12h to obtain a mixed solution, then the mixed solution was suction filtered and washed to remove excess silane coupling agent KH-550 to obtain surface aminated mesoporous silica;

[0053] S2.2: 18 parts by weight of surface aminated mesoporous silica was dissolved in 50 parts by weight of anhydrous ethanol, and 50 parts by weight of silver nitrate solution with a concentration of 0.5 mol / L was added, and stirred in the dark for 4h, then after suction filtration, 70% ethanol washing, deionized water washing and drying, the silver-loaded mesoporous silica material was obtained;

[0054] S3: Preparation of modified mullite fiber,

[0055] S3.1: 40 parts by weight of mullite fiber was dispersed and loosened and then put into 120 parts by weight of acetone solution, and ultrasonic dispersion was carried out for 2h, and after washing and drying, the dried mullite fiber was put into 150 parts by weight of sodium hydroxide solution with a concentration of 1 mol / L, and heated at 80°C for 2h, and after washing and drying, the pretreated mullite fiber was obtained;

[0056] S3.2: Put the pretreated mullite fibers into a 10% mass fraction silane coupling agent KH-550 aqueous solution, the solid-liquid mass ratio of the pretreated mullite fibers to the 10% mass fraction silane coupling agent KH-550 aqueous solution is 4:25, heat in a water bath at 65℃ for 4h, after heating, filter, wash 5 times with deionized water, dry, and obtain modified mullite fibers;

[0057] S4: Pipe material granule processing and high-strength ceramic core antibacterial pipe material preparation,

[0058] S4.1: Mix the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin according to the proportion, the mixing ratio of the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin is 3:3:50, stir and mix for 10min with a high-speed mixer, then extrude and granulate by using a double-screw extruder, the extrusion temperature is 230℃, and antibacterial inner layer granules are obtained;

[0059] S4.2: Mix the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP according to the proportion, the mixing mass ratio of the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP is 140:40:12:8:1.5:1, stir and mix for 10min with a high-speed mixer, then extrude and granulate by using a double-screw extruder, the extrusion temperature is 230℃, and heat-resistant outer layer granules are obtained;

[0060] S4.3: Extrude the antibacterial inner layer granules into a single-screw extruder, the extrusion temperature is 240℃, and the rotating speed is 60r / min, and antibacterial inner tube is obtained;

[0061] S4.4: Extrude the heat-resistant outer layer granules into another single-screw extruder, the extrusion temperature is 240℃, and the rotating speed is 90r / min, and heat-resistant outer tube is obtained;

[0062] S4.5: Put the antibacterial inner tube and the heat-resistant outer tube into a co-extrusion device for co-extrusion, place the extruded material in a molding die for molding, and after shaping, cooling, traction and cutting, a high-strength ceramic core antibacterial pipe material is obtained.

[0063] Example 2

[0064] A preparation process of a high-strength ceramic core antibacterial pipe material, specifically comprising the following steps:

[0065] S1: Preparation of antibacterial glass fiber,

[0066] S1.1: 48 parts by weight of 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, 15 parts by weight of ethyl silicate and 70 parts by weight of anhydrous ethanol were stirred and mixed, then 130 parts by weight of deionized water was added, and stirred at 25°C for 2h to obtain an antibacterial treatment solution;

[0067] S1.2: The glass fiber was added to the hydrogen peroxide solution with a concentration of 0.1 mol / L, wherein the length of the glass fiber was 60 μm, the diameter was 20 μm, and the solid-liquid mass ratio of the glass fiber to the hydrogen peroxide solution with a concentration of 0.1 mol / L was 7:20, and stirred at 60°C for 15 min. Then, the oxidized glass fiber was taken out and completely immersed in the titanate coupling agent for 40 min. After filtration, washing and drying, the pretreated glass fiber was obtained.

[0068] S1.3: The pretreated glass fiber was completely immersed in the antibacterial treatment solution, and the mass ratio of the pretreated glass fiber to the antibacterial treatment was 1:7. After stirring for 20 min, it was left at room temperature for 30 min. Then, the treated glass fiber was taken out and placed in an oven at 100°C for grafting reaction for 1h. After the reaction, the reacted glass fiber was taken out, washed with deionized water for 2 times, and then placed in a drying oven at 65°C for 30 min to obtain the antibacterial glass fiber.

[0069] S2: Preparation of silver-loaded mesoporous silica material,

[0070] S2.1: 21 parts by weight of mesoporous silica was dissolved in 90 parts by weight of anhydrous ethanol, and 24 parts by weight of silane coupling agent KH-550 was added dropwise, and stirred and refluxed for 8h to obtain a mixed solution. Then, the mixed solution was suction filtered and washed to remove excess silane coupling agent KH-550 to obtain surface aminated mesoporous silica.

[0071] S2.2: 18 parts by weight of surface aminated mesoporous silica was dissolved in 50 parts by weight of anhydrous ethanol, and 50 parts by weight of silver nitrate solution with a concentration of 0.5 mol / L was added, and stirred in the dark for 3h. Then, after suction filtration, ethanol with a volume fraction of 70% was used for washing, deionized water was used for washing, and drying was performed to obtain the silver-loaded mesoporous silica material.

[0072] S3: Preparation of modified mullite fiber,

[0073] S3.1: 40 parts by weight of mullite fiber was dispersed and loosened, and then placed in 120 parts by weight of acetone solution, and ultrasonic dispersed for 1h. After washing and drying, the dried mullite fiber was placed in 150 parts by weight of sodium hydroxide solution with a concentration of 1 mol / L, and heated at 70°C for 1h. After washing and drying, the pretreated mullite fiber was obtained.

[0074] S3.2: Put the pretreated mullite fibers into a 10% mass fraction of silane coupling agent KH-550 aqueous solution, the solid-liquid mass ratio of the pretreated mullite fibers to the 10% mass fraction of silane coupling agent KH-550 aqueous solution is 4:25, heated in a water bath at 50℃ for 2h, after heating, filter, wash twice with deionized water, dry, and obtain modified mullite fibers;

[0075] S4: Pipe material granule processing and high-strength ceramic core antibacterial pipe material preparation,

[0076] S4.1: Mix the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin according to the proportion, the mixing ratio of the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin is 3:3:50, stir and mix for 5min with a high-speed mixer, then extrude and granulate with a twin-screw extruder, the extrusion temperature is 180℃, and obtain antibacterial inner layer granules;

[0077] S4.2: Mix the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP according to the proportion, the mixing mass ratio of the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP is 140:40:12:8:1.5:1, stir and mix for 10min with a high-speed mixer, then extrude and granulate with a twin-screw extruder, the extrusion temperature is 200℃, and obtain heat-resistant outer layer granules;

[0078] S4.3: Extrude the antibacterial inner layer granules into a single-screw extruder, the extrusion temperature is 180℃, and the rotating speed is 40r / min, and obtain an antibacterial inner tube;

[0079] S4.4: Extrude the heat-resistant outer layer granules into another single-screw extruder, the extrusion temperature is 180℃, and the rotating speed is 60r / min, and obtain a heat-resistant outer tube;

[0080] S4.5: Put the antibacterial inner tube and the heat-resistant outer tube into a co-extrusion device for co-extrusion, place the extruded material into a molding die for molding, and obtain a high-strength ceramic core antibacterial pipe material after shaping, cooling, pulling and cutting.

[0081] Example 3

[0082] A preparation process of a high-strength ceramic core antibacterial pipe material, specifically comprising the following steps:

[0083] S1: Preparation of antibacterial glass fiber,

[0084] S1.1: 20 parts by weight of 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride, 4 parts by weight of tetraethyl orthosilicate and 50 parts by weight of anhydrous ethanol were stirred and mixed, then 80 parts by weight of deionized water was added, and stirred at 35℃ for 4h to obtain an antibacterial treatment solution;

[0085] S1.2: The glass fiber was added to the hydrogen peroxide solution with a concentration of 0.1 mol / L, wherein the length of the glass fiber was 60 μm, the diameter was 20 μm, and the solid-liquid mass ratio of the glass fiber to the hydrogen peroxide solution with a concentration of 0.1 mol / L was 1:10, and stirred at 85℃ for 30 min, then the oxidized glass fiber was taken out and completely immersed in the titanate coupling agent for 80 min, and after filtration, washing and drying, the pretreated glass fiber was obtained;

[0086] S1.3: The pretreated glass fiber was completely immersed in the antibacterial treatment solution, and the mass ratio of the pretreated glass fiber to the antibacterial treatment was 1:30, and after stirring for 40 min, it was placed at room temperature for 60 min, then the treated glass fiber was taken out and placed in an oven at 120℃ for grafting reaction for 2h, after the reaction was completed, the reacted glass fiber was taken out, washed with deionized water for 3 times, and then placed in an oven at 85℃ for drying for 60 min, to obtain the antibacterial glass fiber;

[0087] S2: Preparation of silver-loaded mesoporous silica material,

[0088] S2.1: 12 parts by weight of mesoporous silica was dissolved in 40 parts by weight of anhydrous ethanol, 15 parts by weight of silane coupling agent KH-550 was added dropwise, and stirred and refluxed for 12h to obtain a mixed solution, then the mixed solution was suction filtered and washed to remove excess silane coupling agent KH-550, to obtain surface aminated mesoporous silica;

[0089] S2.2: 5 parts by weight of surface aminated mesoporous silica was dissolved in 20 parts by weight of anhydrous ethanol, then 20 parts by weight of silver nitrate solution with a concentration of 0.5 mol / L was added, and stirred in the dark for 4h, then after suction filtration, ethanol with a volume fraction of 70% was used for washing, deionized water was used for washing, and drying was performed, to obtain the silver-loaded mesoporous silica material;

[0090] S3: Preparation of modified mullite fiber,

[0091] S3.1: 30 parts by weight of mullite fiber was dispersed and loosened, then placed in 60 parts by weight of acetone solution, and ultrasonic dispersed for 2h, then after washing and drying, the dried mullite fiber was placed in 80 parts by weight of sodium hydroxide solution with a concentration of 1 mol / L, and heated at 80℃ for 2h, then after washing and drying, the pretreated mullite fiber was obtained;

[0092] S3.2: Put the pretreated mullite fibers into a 10% mass fraction of silane coupling agent KH-550 aqueous solution, the solid-liquid mass ratio of pretreated mullite fibers to 10% mass fraction of silane coupling agent KH-550 aqueous solution is 1:20, heated in a water bath at 65℃ for 4h, after heating, filter, wash 5 times with deionized water, dry, get modified mullite fibers;

[0093] S4: Pipe material granule processing and high-strength ceramic core antibacterial pipe material preparation,

[0094] S4.1: Mix the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin according to the proportion, the mixing ratio of the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin is 1:1:45, stir and mix for 10min with a high-speed mixer, then extrude and granulate with a twin-screw extruder, the extrusion temperature is 230℃, to obtain antibacterial inner layer granules;

[0095] S4.2: Mix the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP according to the proportion, the mixing mass ratio of the polypropylene resin, modified mullite fiber, color masterbatch, polypropylene grafted maleic anhydride, stearate and antioxidant DLTP is 80:20:3:3:0.5:0.5, stir and mix for 10min with a high-speed mixer, then extrude and granulate with a twin-screw extruder, the extrusion temperature is 230℃, to obtain heat-resistant outer layer granules;

[0096] S4.3: Extrude the antibacterial inner layer granules into a single-screw extruder, the extrusion temperature is 240℃, the rotation speed is 60r / min, to obtain an antibacterial inner tube;

[0097] S4.4: Extrude the heat-resistant outer layer granules into another single-screw extruder, the extrusion temperature is 240℃, the rotation speed is 90r / min, to obtain a heat-resistant outer tube;

[0098] S4.5: Put the antibacterial inner tube and the heat-resistant outer tube into a co-extrusion device for co-extrusion, place the extruded material into a molding die for molding, after shaping, cooling, pulling and cutting, obtain a high-strength ceramic core antibacterial pipe material.

[0099] Comparative Example 1

[0100] Comparative Example 1 is different from Example 1 in that the antibacterial glass fiber in step S4.1 is removed, and the remaining steps remain unchanged, to prepare a high-strength ceramic core antibacterial pipe material, which is denoted as Comparative Example 1.

[0101] Comparative Example 2

[0102] Comparative Example 2 is different from Example 1 in that the silver loaded mesoporous silica material in step S4.1 is removed, and the rest of the steps remain unchanged, to prepare high-strength ceramic core antibacterial pipe material, which is denoted as Comparative Example 2.

[0103] Comparative Example 3

[0104] Comparative Example 3 is different from Example 1 in that the antibacterial type glass fiber in step S4.1 is replaced by organosilicon quaternary ammonium salt, and the rest of the steps remain unchanged, to prepare high-strength ceramic core antibacterial pipe material, which is denoted as Comparative Example 3.

[0105] Comparative Example 4

[0106] Comparative Example 4 is different from Example 1 in that the modified mullite fiber in step S4.2 is removed, and the rest of the steps remain unchanged, to prepare high-strength ceramic core antibacterial pipe material, which is denoted as Comparative Example 4.

[0107] One of the high-strength ceramic core antibacterial pipe materials prepared from Examples 1-3 and Comparative Examples 1-3 is selected as a sample, the sample is cut from the center and cut into 5 cm pipe pieces as test samples. According to the method specified in the standard JC / T 939-2004 "Antibacterial Performance of Antibacterial Plastic Pipes for Building", the test samples are tested for antibacterial performance and antibacterial durability performance, and the durability test is to immerse the test samples in a deionized water bath at a temperature of 50°C for 24h, and then detect the antibacterial performance of the test samples on Escherichia coli and Staphylococcus aureus. The results are shown in Table 1.

[0108] Table 1: Test results of antibacterial performance and antibacterial durability performance

[0109]

[0110] As can be seen from Table 1, the high-strength porcelain core antibacterial pipe material prepared in Examples 1-3 has an antibacterial rate of greater than 99% for E. coli and S. aureus, and after the durability immersion treatment, the antibacterial rate can still be maintained at more than 99%, having strong antibacterial performance and strong antibacterial durability. In contrast, the high-strength porcelain core antibacterial pipe material in Comparative Examples 1-3 also has antibacterial performance, but the antibacterial rate and the antibacterial rate after durability treatment are less than those of the high-strength porcelain core antibacterial pipe material in Examples 1-3, indicating that the addition of antibacterial glass fibers or silver-loaded mesoporous silica material in the antibacterial inner pipe of the high-strength porcelain core antibacterial pipe material can play a role in the antibacterial effect of E. coli and S. aureus, but the use of the two in combination can have a synergistic effect, so that the high-strength porcelain core antibacterial pipe material has strong antibacterial performance. In addition, after the durability immersion treatment, the test samples of Comparative Examples 2-3 have a significant decrease in antibacterial effect on E. coli and S. aureus, indicating that the use of silver-loaded mesoporous silica material and the loading of organosilicon quaternary ammonium salt in glass fibers can help to improve the antibacterial durability of the high-strength porcelain core antibacterial pipe material on E. coli and S. aureus, so that the high-strength porcelain core antibacterial pipe material has a high and persistent antibacterial effect.

[0111] The high-strength porcelain core antibacterial pipe material prepared in Examples 1-3 and Comparative Example 4 was tested for flame retardancy, thermal insulation, and linear expansion coefficient, wherein the flame retardancy was tested by GB / T2406.2-2009 method, the thermal insulation was tested by GB / T5990 method, and the linear expansion coefficient was tested by GB / T1036 method. The test results are shown in Table 2.

[0112] Table 2: Test results of flame retardancy, thermal insulation, and linear expansion coefficient

[0113] Group Oxygen index LOI (%) Thermal conductivity (W / (m*K)) Linear expansion coefficient (pm / (m*°C)) Example 1 36.24 0.07 2.5 Example 2 35.68 0.1 2.9 Example 3 36.06 0.08 2.7 Comparative Example 4 Example 5 32.51 0.14 5.6

[0114] As can be seen from Table 2, the high-strength porcelain core antibacterial pipe material prepared in Examples 1-3 has an oxygen index test result greater than that of Comparative Example 4, and a thermal conductivity coefficient and linear expansion coefficient test result less than that of Comparative Example 3, indicating that the high-strength porcelain core antibacterial pipe material of Examples 1-3 has good flame retardant performance, thermal insulation performance, and thermal dimensional stability. The addition of modified mullite fibers can effectively improve the linear expansion coefficient and thermal conductivity coefficient of the high-strength porcelain core antibacterial pipe material, thereby reducing the deformation of the pipe after heating.

[0115] It should be understood that those of ordinary skill in the art can make improvements or changes based on the above description, and all such improvements and changes shall fall within the scope of protection of the appended claims of the present application. Parts not described in detail in the specification belong to the prior art known to those skilled in the art.

Claims

1. A high strength porcelain core antibacterial pipe, characterized by, The application relates to an antibacterial inner tube and a heat-resistant outer tube. The raw material of the antibacterial inner tube comprises antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin, and the mixing mass ratio of the antibacterial glass fiber, the silver-loaded mesoporous silica material and the polypropylene resin is (1-3):(1-3):(45-50). The raw material of the antibacterial glass fiber comprises pretreated glass fiber and an antibacterial treatment solution, and the mass ratio of the pretreated glass fiber to the antibacterial treatment solution is (1-10):(30-70); the pretreated glass fiber is obtained by sequentially treating glass fiber with hydrogen peroxide and a titanate coupling agent. The raw material of the antibacterial treatment solution comprises 20-48 parts by weight of organosilicon quaternary ammonium salt, 4-15 parts by weight of ethyl silicate, 50-70 parts by weight of anhydrous ethanol and 80-130 parts by weight of deionized water. The raw material of the silver-loaded mesoporous silica material comprises 5-18 parts by weight of surface-aminoized mesoporous silica, 20-50 parts by weight of anhydrous ethanol and 20-50 parts by weight of a silver nitrate solution with a concentration of 0.5 mol / L; the surface-aminoized mesoporous silica is obtained by modifying mesoporous silica with a silane coupling agent KH-550 after the mesoporous silica is dissolved in anhydrous ethanol. The raw material of the heat-resistant outer tube comprises polypropylene resin, modified mullite fiber, color masterbatch, compatibilizer, lubricant and antioxidant, and the mass ratio of the polypropylene resin, the modified mullite fiber, the color masterbatch, the compatibilizer, the lubricant and the antioxidant is (80-140):(20-40):(3-12):(3-8):(0.5-1.5):(0.5-1). The raw material of the modified mullite fiber comprises pretreated mullite fiber and a 10% silane coupling agent KH-550 aqueous solution, and the solid-liquid mass ratio is (1-8):(20-50). The raw material of the pretreated mullite fiber comprises 30-40 parts by weight of mullite fiber, 60-120 parts by weight of an acetone solution and 80-150 parts by weight of a sodium hydroxide solution with a concentration of 1 mol / L.

2. A process for the preparation of high strength ceramic core antibacterial pipe as claimed in claim 1 wherein, The application further discloses a preparation method of the antibacterial inner tube and the heat-resistant outer tube. S1: antibacterial glass fiber preparation; an antibacterial treatment solution is prepared by mixing organosilicon quaternary ammonium salt, ethyl silicate, anhydrous ethanol and deionized water; pretreated glass fiber is prepared by sequentially treating glass fiber with hydrogen peroxide and a titanate coupling agent; the pretreated glass fiber is soaked in the antibacterial treatment solution, and stirring, standing, high-temperature reaction, washing and drying are carried out to obtain the antibacterial glass fiber; S2: silver-loaded mesoporous silica material preparation; surface-aminoized mesoporous silica is obtained by modifying mesoporous silica with a silane coupling agent KH-550 after the mesoporous silica is dissolved in anhydrous ethanol; the surface-aminoized mesoporous silica is dissolved in anhydrous ethanol, and a silver nitrate solution is added; the mixture is stirred in the dark and sealed, and then is subjected to filtration, washing and drying to obtain the silver-loaded mesoporous silica material. S3: modification of mullite fiber preparation, the mullite fiber is put into the acetone solution, after ultrasonic dispersion, washing and drying, the dried mullite fiber is put into sodium hydroxide solution, after heating, washing and drying, the pretreated mullite fiber is obtained, the pretreated mullite fiber is put into silane coupling agent KH-550 aqueous solution, water bath heating reaction, after filtration, washing and drying, the modified mullite fiber is obtained; S4: pipe material granule processing and high strength ceramic core antibacterial pipe material preparation, the antibacterial glass fiber, silver loaded mesoporous silica material and polypropylene resin are stirred and mixed in proportion, and the antibacterial inner layer granule is obtained by granulation, the polypropylene resin, modified mullite fiber, color masterbatch, compatibilizer, lubricant and antioxidant are stirred and mixed in proportion, and the heat resistant outer layer granule is obtained by granulation, the antibacterial inner layer granule and the heat resistant outer layer granule are extruded to pipe respectively, and the antibacterial inner pipe and the heat resistant outer pipe are obtained, after co-extrusion, shaping and setting, cooling, traction and cutting, the high strength ceramic core antibacterial pipe material is obtained.

3. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 2 wherein, The organosilicon quaternary ammonium salt is 3-(trimethoxysilyl) propyldimethyloctadecyl ammonium chloride, 3-(trimethoxysilyl) propyltrimethyl ammonium chloride, 3-(triethoxysilyl) propyldimethyloctadecyl ammonium chloride or 3-(trihydroxysilylpropyl) dimethyloctadecyl ammonium chloride.

4. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 2 wherein, Step S1 antibacterial glass fiber preparation, specifically including the following steps: S1.1: 20-48 parts by weight of organosilicon quaternary ammonium salt, 4-15 parts by weight of tetraethyl orthosilicate and 50-70 parts by weight of anhydrous ethanol are stirred and mixed, then 80-130 parts by weight of deionized water is added, and stirred at 25-35℃ for 2-4h to obtain an antibacterial treatment solution; S1.2: the glass fiber is added to the hydrogen peroxide solution with a concentration of 0.1mol / L, and the solid-liquid mass ratio of the glass fiber to the hydrogen peroxide solution with a concentration of 0.1mol / L is (1-7):(10-20), and stirred at 60-85℃ for 15-30min, then the oxidized glass fiber is taken out and completely immersed in the titanate coupling agent for 40-80min, after filtration, washing and drying, the pretreated glass fiber is obtained; S1.3: the pretreated glass fiber is completely immersed in the antibacterial treatment solution, and the mass ratio of the pretreated glass fiber to the antibacterial treatment is (1-10):(30-70), after stirring for 20-40min, it is left at room temperature for 30-60min, then the treated glass fiber is taken out and placed in an oven at 100-120℃ for grafting reaction for 1-2h, after the reaction is completed, the reacted glass fiber is taken out, washed with deionized water for 1-3 times, and then dried in an oven at 65-85℃ for 30-60min to obtain the antibacterial glass fiber.

5. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 4 wherein, The length of the glass fiber is 50-100μm, and the diameter is 10-30μm.

6. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 2 wherein, Step S2 silver loaded mesoporous silica material preparation, specifically including the following steps: S2.1: 12-21 parts by weight of mesoporous silica is dissolved in 40-90 parts by weight of anhydrous ethanol, 15-24 parts by weight of silane coupling agent KH-550 is added dropwise, and stirring reflux is carried out for 8-12 hours to obtain a mixed solution, and then the mixed solution is filtered, washed and dried to obtain surface aminated mesoporous silica; S2.2: 5-18 parts by weight of surface aminated mesoporous silica is dissolved in 20-50 parts by weight of anhydrous ethanol, and 20-50 parts by weight of a silver nitrate solution with a concentration of 0.5 mol / L is added, and stirring is carried out in the dark for 3-4 hours, and then the mixture is filtered, washed with 70% ethanol and deionized water, and dried to obtain a silver-loaded mesoporous silica material.

7. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 2 wherein, Step S3 modification of mullite fiber preparation, specifically comprising the following steps: S3.1: 30-40 parts by weight of mullite fiber is placed in 60-120 parts by weight of acetone solution, ultrasonic dispersion is carried out for 1-2 hours, and then the mullite fiber is washed and dried, and the dried mullite fiber is placed in 80-150 parts by weight of a 1 mol / L sodium hydroxide solution, heated at 70-80°C for 1-2 hours, and then washed and dried to obtain pretreated mullite fiber; S3.2: The pretreated mullite fiber is placed in a 10% silane coupling agent KH-550 aqueous solution, the solid-liquid mass ratio of the pretreated mullite fiber to the 10% silane coupling agent KH-550 aqueous solution is (1-8):(20-50), and water bath heating is carried out at 50-65°C for 2-4 hours, after heating, the mixture is filtered, washed with deionized water for 2-5 times, and dried to obtain modified mullite fiber.

8. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 2 wherein, Step S4 pipe granule processing and high-strength ceramic core antibacterial pipe preparation, specifically comprising the following steps: S4.1: The antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin are mixed in proportion, the mixing ratio of the antibacterial glass fiber, silver-loaded mesoporous silica material and polypropylene resin is (1-3):(1-3):(45-50), and high-speed stirring is carried out for 5-10 minutes, and then a double-screw extruder is used for extrusion granulation, the extrusion temperature is 180-230°C, and an antibacterial inner layer granule is obtained; S4.2: The polypropylene resin, modified mullite fiber, color masterbatch, compatibilizer, lubricant and antioxidant are mixed in proportion, the mixing mass ratio of the polypropylene resin, modified mullite fiber, color masterbatch, compatibilizer, lubricant and antioxidant is (80-140):(20-40):(3-12):(3-8):(0.5-1.5):(0.5-1), and high-speed stirring is carried out for 5-10 minutes, and then a double-screw extruder is used for extrusion granulation, the extrusion temperature is 200-230°C, and a heat-resistant outer layer granule is obtained; S4.3: The antibacterial inner layer granule is put into a single-screw extruder for extrusion to obtain an antibacterial inner tube; S4.4: The heat-resistant outer layer granule is put into another single-screw extruder for extrusion to obtain a heat-resistant outer tube; S4.5: the antibacterial inner tube and the heat-resistant outer tube are put into a co-extrusion device for co-extrusion, the extruded material is put into a forming mold for forming, and after shaping, cooling, pulling and cutting, a high-strength antibacterial porcelain core pipe is obtained.

9. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 8 wherein, The compatilizer is polypropylene grafted maleic anhydride or glycidyl methacrylate, the lubricant is fatty acid amide, stearate or polyethylene wax, and the antioxidant is antioxidant DLTP, antioxidant 1010 or antioxidant 168.

10. The process for the preparation of high strength vitreous core antibacterial pipe as claimed in claim 9 wherein, The single screw extruder in step S4.3 has an extrusion temperature of 180-240 DEG C and a rotating speed of 40-60 r / min, and the single screw extruder in step S4.4 has an extrusion temperature of 180-240 DEG C and a rotating speed of 60-90 r / min.

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