阅读说明：本技术 一种抗菌防藻防变色水培槽材料及其制备方法 (Antibacterial, algae-proof and anti-discoloration water culture tank material and preparation method thereof ) 是由 郑凌然 徐沛佩 王艳 徐明铭 于 2020-10-28 设计创作，主要内容包括：本发明提出了一种抗菌防藻防变色水培槽材料,其包括下述原料：聚丙烯100份、防变色抗菌防藻剂0.5-10份、无机填料0-20份、弹性体1-10份、偶联剂0.1-2份、抗氧剂0.1-2份、添加剂0-3份；其中,所述防变色抗菌防藻剂是由以离子交换法制备的载银、铜沸石和包覆在其表面的二氧化硅薄膜组成。本发明通过在聚丙烯基体中添加防变色抗菌防藻剂,使材料具有抗菌防藻性能的同时,避免了材料在加工、存储、使用时发生变色。(The invention provides an antibacterial, anti-algae and anti-discoloration water culture tank material which comprises the following raw materials: 100 parts of polypropylene, 0.5-10 parts of anti-discoloration antibacterial anti-algae agent, 0-20 parts of inorganic filler, 1-10 parts of elastomer, 0.1-2 parts of coupling agent, 0.1-2 parts of antioxidant and 0-3 parts of additive; the antitarnish antibacterial algaecide consists of silver-carrying zeolite prepared by an ion exchange method, copper zeolite and a silicon dioxide film coated on the surface of the silver-carrying zeolite. According to the invention, the antitarnish antibacterial algicide is added into the polypropylene matrix, so that the material has antibacterial and algicide properties, and the material is prevented from discoloring during processing, storage and use.)

1. The antibacterial, algae-proof and discoloration-preventing water culture tank material is characterized by comprising the following raw materials in parts by weight: 100 parts of polypropylene, 0.5-5 parts of anti-discoloration antibacterial anti-algae agent, 0-20 parts of inorganic filler, 1-10 parts of elastomer, 0.1-2 parts of coupling agent, 0.1-2 parts of antioxidant and 0-3 parts of additive;

the antitarnish antibacterial algaecide consists of silver-carrying zeolite prepared by an ion exchange method, copper zeolite and a silicon dioxide film coated on the surface of the silver-carrying zeolite.

2. The antibacterial, anti-algae and anti-discoloration water culture tank material according to claim 1, wherein the polypropylene is a polypropylene having a melt flow rate of 0.5-60g/10min at 230 ℃ under a load of 2.16 kg.

3. The antibacterial, anti-algae and anti-discoloration water culture tank material according to any one of claims 1 to 2, wherein the anti-discoloration, antibacterial and anti-algae agent is obtained by exchanging silver ions and copper ions with a mixed solution of zeolite, silver salt and copper salt, and then reacting with tetraethyl orthosilicate.

4. The antibacterial of claim 3The algae-proof and discoloration-proof water culture tank material is characterized in that the zeolite isOne or more of artificial zeolite, X-type artificial zeolite, Y-type artificial zeolite or mordenite.

5. The antibacterial, anti-algae and anti-discoloration water culture tank material according to claim 3 or 4, wherein the silver salt is one or more of silver nitrate, silver sulfate or silver chloride, and the copper salt is one or more of copper nitrate, copper sulfate or copper chloride; preferably, the molar ratio of the amounts of silver salt and copper salt is 0.1-0.3: 0.1-3.

6. The antibacterial, anti-algae and anti-discoloration water culture tank material according to any one of claims 3 to 5, wherein the dosage ratio of the zeolite to the mixed solution of silver salt and copper salt is 0.5-1.5g:10mL, and the dosage ratio of the zeolite to tetraethyl orthosilicate is 4-20g:1 mL.

7. The antibacterial, algae-proof and discoloration-preventing water culture tank material according to any one of claims 1 to 6, wherein said inorganic filler is one or more of talc, barium sulfate or calcium carbonate; the elastomer is a copolymer of ethylene and octene; the coupling agent is one or a mixture of silane coupling agent, titanate coupling agent or aluminate coupling agent; the antioxidant is one or a mixture of hindered phenol antioxidants or thioester antioxidants.

8. The antibacterial, anti-algae and anti-discoloration water culture tank material according to any one of claims 1 to 7, wherein said additives comprise a lubricant, a light stabilizer;

preferably, the lubricant is one or more of stearate, amide, silicone or metal soap, and the light stabilizer is one or more of triazine light stabilizer, benzotriazole, salicylate or hindered amine light stabilizer.

9. A preparation method of an antibacterial, algae-proof and discoloration-preventing water culture tank material is characterized by comprising the following steps: uniformly mixing raw materials of polypropylene, the anti-discoloration antibacterial anti-algae agent, the inorganic filler, the elastomer, the coupling agent, the antioxidant and the additive in a high-speed mixer, adding the raw materials into a double-screw extruder for melt extrusion, and then cooling and granulating to obtain the anti-bacterial anti-algae discoloration water culture tank material.

10. The preparation method of the antibacterial, anti-algae and anti-discoloration water culture tank material according to claim 9, wherein the melt extrusion process conditions comprise: the first region is 180 ℃ minus 190 ℃, the second region is 190 ℃ minus 200 ℃, the third region is 200 ℃ minus 210 ℃, and the fourth region is 190 ℃ minus 200 ℃.

Technical Field

The invention relates to the technical field of materials, in particular to an antibacterial, algae-proof and discoloration-preventing water culture tank material and a preparation method thereof.

Background

Fungi or algae in water have long plagued practitioners in the water culture and breeding field. For example, algae growth can create problems, where the algae can consume nutrients accumulated in the water and can be harmful to the hydroponic plants or animals. In the past, the treatment method generally comprises removing algae, or culturing algae in a container or adding quicklime into the algae for disinfection, but the method is not the fundamental method.

At present, practitioners develop water culture tank materials with the functions of preventing bacteria and algae to achieve the effect of preventing bacteria and algae from growing and breeding, so that the culture solution is protected. However, the prepared water culture tank material is usually prepared by adding an antibacterial and anti-algae additive into a base material, and because metal ions contained in the antibacterial and anti-algae additive change color when being exposed to light or heat, the color of a final product is easy to turn yellow, and the antibacterial and anti-algae effect is not durable.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides an antibacterial, anti-algae and anti-discoloration water culture tank material and a preparation method thereof.

The invention provides an antibacterial and anti-algae discoloration prevention hydroponic tank material which comprises the following raw materials in parts by weight: 100 parts of polypropylene, 0.5-5 parts of anti-discoloration antibacterial anti-algae agent, 0-20 parts of inorganic filler, 1-10 parts of elastomer, 0.1-2 parts of coupling agent, 0.1-2 parts of antioxidant and 0-3 parts of additive;

the antitarnish antibacterial algaecide consists of silver-carrying zeolite prepared by an ion exchange method, copper zeolite and a silicon dioxide film coated on the surface of the silver-carrying zeolite.

Preferably, the polypropylene is a polypropylene having a melt flow rate of 0.5 to 60g/10min at 230 ℃ under a load of 2.16 kg.

Preferably, the discoloration-preventing antibacterial algicide is obtained by exchanging silver ions and copper ions with a mixed solution of zeolite, silver salt and copper salt, and then reacting with tetraethyl orthosilicate.

Preferably, the zeolite isOne or more of artificial zeolite, X-type artificial zeolite, Y-type artificial zeolite or mordenite.

Preferably, the silver salt is one or more of silver nitrate, silver sulfate or silver chloride, and the copper salt is one or more of copper nitrate, copper sulfate or copper chloride; preferably, the molar ratio of the amounts of silver salt and copper salt is 0.1-0.3: 0.1-3.

Preferably, the dosage ratio of the zeolite to the mixed solution of the silver salt and the copper salt is 0.5-1.5g:10mL, and the dosage ratio of the zeolite to the tetraethyl orthosilicate is 4-20g:1 mL.

Preferably, the inorganic filler is one or more of talcum powder, barium sulfate or calcium carbonate; the elastomer is a copolymer of ethylene and octene; the coupling agent is one or a mixture of silane coupling agent, titanate coupling agent or aluminate coupling agent; the antioxidant is one or a mixture of hindered phenol antioxidants or thioester antioxidants.

Preferably, the additives include lubricants, light stabilizers;

preferably, the lubricant is one or more of stearate, amide, silicone or metal soap, and the light stabilizer is one or more of triazine light stabilizer, benzotriazole, salicylate or hindered amine light stabilizer.

The invention also provides a preparation method of the antibacterial, algae-proof and anti-discoloration water culture tank material, which comprises the following steps: uniformly mixing raw materials of polypropylene, the anti-discoloration antibacterial anti-algae agent, the inorganic filler, the elastomer, the coupling agent, the antioxidant and the additive in a high-speed mixer, adding the raw materials into a double-screw extruder for melt extrusion, and then cooling and granulating to obtain the anti-bacterial anti-algae discoloration water culture tank material.

Preferably, the process conditions of the melt extrusion include: the first region is 180 ℃ minus 190 ℃, the second region is 190 ℃ minus 200 ℃, the third region is 200 ℃ minus 210 ℃, and the fourth region is 190 ℃ minus 200 ℃.

In the antibacterial, algae-preventing and discoloration-preventing water culture tank material, polypropylene is used as a matrix raw material, and a discoloration-preventing antibacterial agent is added, wherein the discoloration-preventing antibacterial agent comprises copper and silver active components, and has the characteristics of high efficiency prevention of algae growth by copper compounds and strong bactericidal capability by silver compounds, so that the polypropylene composite material is endowed with excellent antibacterial and algae-preventing activity on the basis of the original performance of the polypropylene material.

Furthermore, the discoloration-prevention antibacterial algaecide provided by the invention is prepared by exchanging silver ions and copper ions with a mixed solution of zeolite, silver salt and copper salt, and then adding tetraethyl orthosilicate for reaction, so that a layer of silicon dioxide film is covered on the surface of the silver-and copper-loaded zeolite, and the silicon dioxide film plays a role in protection, can anchor the silver and copper ions on ion exchange positions, fully reduces the dissolution rate of the silver and copper ions from a carrier, and prevents the silver ions from discoloring due to too early and too fast contact with light and heat and prevents the copper ions from being rapidly separated out, so that the material is prevented from discoloring due to water absorption. Therefore, the long-term and lasting algae-proof and antibacterial effects of the water culture tank material are ensured, and the possibility of color change of the water culture tank material is also prevented.

Detailed Description

Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.

Example 1

An antibacterial, algae-proof and anti-discoloration water culture tank material comprises the following raw material components in parts by weight: 100 parts of copolymerized propylene (ethylene/propylene block copolymer, the melt flow rate is 26g/10min under the load of 2.16kg at 230 ℃), 2 parts of antitarnish antibacterial algaecide, 5 parts of ethylene-octene copolymer POE (ENGAGE 8207), 0.5 part of silane coupling agent (KH550), 0.5 part of antioxidant (Irgafos168) and 0.5 part of antioxidant (Irganox 1010);

the anti-discoloration antibacterial algaecide comprises silver-loaded and copper zeolite and a silicon dioxide film coated on the surfaces of the silver-loaded and copper zeolite, and is prepared by the following method: will be provided withArtificial zeolite is dried at 300 DEG CDrying for 2h, adding the mixture into a mixed solution containing silver nitrate and copper nitrate (0.2 mol/L of silver nitrate and 1mol/L of copper nitrate), stirring for 4h at 70 ℃ according to a solid-to-liquid ratio of 1g/10mL, after the reaction is finished, centrifugally separating, washing with deionized water, drying at 100 ℃, and grinding into powder to obtain silver-loaded and copper-loaded zeolite; adding silver-carrying zeolite, copper zeolite and tetraethyl orthosilicate into ethanol according to the weight-volume ratio of 10g:1mL, stirring for 1h at room temperature, dropwise adding ammonia water (0.15mol/L) which is 2 times of the volume of the tetraethyl orthosilicate, stirring for reaction for 4h at 50 ℃, filtering, washing with ethanol and deionized water, and drying at 100 ℃ to obtain the discoloration-preventing antibacterial algaecide.

The antibacterial, algae-proof and discoloration-preventing water culture tank material is prepared by the following method: adding 100 parts by weight of the above-mentioned propylene copolymer, 2 parts by weight of an antitarnish antibacterial algaecide, 5 parts by weight of an ethylene-octene copolymer, 0.5 part by weight of a silane coupling agent and 1 part by weight of an antioxidant into a high-speed mixer, and mixing for 15min to obtain a mixture; and adding the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a screw cylinder is 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 200 ℃ in the fourth region, and the rotating speed of the double-screw extruder is 500r/min, so as to obtain the antibacterial, algae-preventing and discoloration-preventing water culture tank material.

Example 2

An antibacterial, algae-proof and anti-discoloration water culture tank material comprises the following raw material components in parts by weight: 100 parts of copolymerized propylene (ethylene/propylene block copolymer, the melt flow rate is 26g/10min under the load of 2.16kg at 230 ℃), 0.5 part of antitarnish antibacterial algaecide, 10 parts of talcum powder (the average particle size is 5 mu m), 10 parts of ethylene-octene copolymer POE (ENGAGE 8207), 2 parts of silane coupling agent (KH550), 0.1 part of antioxidant (Irgafos168) and 0.5 part of antioxidant (Irganox 1010);

the anti-discoloration antibacterial algaecide comprises silver-loaded and copper zeolite and a silicon dioxide film coated on the surfaces of the silver-loaded and copper zeolite, and is prepared by the following method: will be provided withThe artificial zeolite was dried at 300 ℃ for 2 hours, and then added to a mixed solution containing silver nitrate and copper nitrate (0.3 mol/L silver nitrate, 0.3mol/L copper nitrate, B/L copper nitrate,3mol/L of copper nitrate), stirring for 4 hours at 70 ℃ according to a solid-to-liquid ratio of 0.5g/10mL, centrifugally separating after the reaction is finished, washing with deionized water, drying at 100 ℃, and grinding into powder to obtain silver-and copper-loaded zeolite; adding silver-carrying zeolite, copper zeolite and tetraethyl orthosilicate into ethanol according to the weight-volume ratio of 20g:1mL, stirring for 1h at room temperature, dropwise adding ammonia water (0.15mol/L) which is 4 times of the volume of the tetraethyl orthosilicate, stirring for reaction for 4h at 50 ℃, filtering, washing with ethanol and deionized water, and drying at 100 ℃ to obtain the discoloration-preventing antibacterial algaecide.

The antibacterial, algae-proof and discoloration-preventing water culture tank material is prepared by the following method: adding 100 parts by weight of the above-mentioned propylene copolymer, 0.5 part by weight of an antitarnish antibacterial algaecide, 10 parts by weight of talcum powder, 10 parts by weight of a copolymer POE of ethylene-octene, 2 parts by weight of a silane coupling agent and 0.6 part by weight of an antioxidant into a high-speed mixer, and mixing for 15min to obtain a mixture; and adding the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a screw cylinder is 190 ℃ in a first area, 200 ℃ in a second area, 200 ℃ in a third area, 190 ℃ in a fourth area, and the rotating speed of the double-screw extruder is 500r/min, so as to obtain the antibacterial, algae-preventing and discoloration-preventing water culture tank material.

Example 3

An antibacterial, algae-proof and anti-discoloration water culture tank material comprises the following raw material components in parts by weight: 100 parts of copolymerized propylene (ethylene/propylene block copolymer, the melt index is 26g/10min under the load of 2.16kg at 230 ℃), 5 parts of antitarnish antibacterial algaecide, 20 parts of talcum powder (the average particle size is 5 mu m), 1 part of ethylene-octene copolymer POE (ENGAGE 8207), 1 part of silane coupling agent (KH550), 1 part of antioxidant (Irgafos168) and 1 part of antioxidant (Irganox 1010);

the anti-discoloration antibacterial algaecide comprises silver-loaded and copper zeolite and a silicon dioxide film coated on the surfaces of the silver-loaded and copper zeolite, and is prepared by the following method: will be provided withThe artificial zeolite was dried at 300 ℃ for 2 hours, added to a mixed solution containing silver nitrate and copper nitrate (0.1 mol/L silver nitrate, 0.1mol/L copper nitrate) and solid-to-liquid ratio of 1.5g/10mL at 70 DEG CStirring for 4h, after the reaction is finished, centrifugally separating, washing with deionized water, drying at 100 ℃, and grinding into powder to obtain silver-loaded and copper-loaded zeolite; adding silver-carrying zeolite, copper zeolite and tetraethyl orthosilicate into ethanol according to the weight-volume ratio of 4g:1mL, stirring for 1h at room temperature, dropwise adding ammonia water (0.15mol/L) which is 2 times of the volume of the tetraethyl orthosilicate, stirring for reaction for 4h at 50 ℃, filtering, washing with ethanol and deionized water, and drying at 100 ℃ to obtain the discoloration-preventing antibacterial algaecide.

The antibacterial, algae-proof and discoloration-preventing water culture tank material is prepared by the following method: adding 100 parts by weight of the above-mentioned propylene copolymer, 5 parts by weight of an antitarnish antibacterial algaecide, 20 parts by weight of talcum powder, 1 part by weight of an ethylene-octene copolymer, 1 part by weight of a silane coupling agent and 2 parts by weight of an antioxidant into a high-speed mixer, and mixing for 15min to obtain a mixture; and adding the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a screw cylinder is 190 ℃ in a first area, 200 ℃ in a second area, 200 ℃ in a third area, 190 ℃ in a fourth area, and the rotating speed of the double-screw extruder is 500r/min, so as to obtain the antibacterial, algae-preventing and discoloration-preventing water culture tank material.

Comparative example 1

The polypropylene composite material comprises the following raw material components in parts by weight: 100 parts of copolymerized propylene (ethylene/propylene block copolymer, melt flow rate of 26g/10min at 230 ℃ under 2.16kg load), 5 parts of ethylene-octene copolymer POE (ENGAGE 8207), 0.5 part of silane coupling agent (KH550), 0.5 part of antioxidant (Irgafos168) and 0.5 part of antioxidant (Irganox 1010);

the polypropylene composite material is prepared by the following method: adding 100 parts by weight of the above-mentioned copolymerized propylene, 5 parts by weight of ethylene-octene copolymer, 0.5 part by weight of silane coupling agent and 1 part by weight of antioxidant into a high-speed mixer, and mixing for 15min to obtain a mixture; and adding the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a screw cylinder is 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 200 ℃ in the fourth region, and the rotating speed of the double-screw extruder is 500r/min, so as to obtain the polypropylene composite material.

Comparative example 2

The polypropylene composite material comprises the following raw material components in parts by weight: 100 parts of copolymerized propylene (ethylene/propylene block copolymer, the melt flow rate is 26g/10min under the load of 2.16kg at 230 ℃), 2 parts of antibacterial algaecide, 5 parts of ethylene-octene copolymer POE (ENGAGE 8207), 0.5 part of silane coupling agent (KH550), 0.5 part of antioxidant (Irgafos168) and 0.5 part of antioxidant (Irganox 1010);

the antibacterial algaecide is silver-loaded and copper-loaded zeolite and is prepared by adopting the following method: will be provided withDrying the artificial zeolite at 300 ℃ for 2h, adding the artificial zeolite into a mixed solution containing silver nitrate and copper nitrate (0.2 mol/L of silver nitrate and 1mol/L of copper nitrate), stirring the mixed solution at 70 ℃ for 4h according to a solid-to-liquid ratio of 1g/10mL, centrifugally separating the mixed solution after the reaction is finished, washing the mixed solution with deionized water, drying the mixed solution at 100 ℃, and grinding the dried mixed solution into powder to obtain the silver-loaded and copper-loaded zeolite.

The polypropylene composite material is prepared by the following method: adding 100 parts by weight of the above-mentioned copolymerized propylene, 2 parts by weight of antibacterial algaecide, 5 parts by weight of ethylene-octene copolymer, 0.5 part by weight of silane coupling agent and 1 part by weight of antioxidant into a high-speed mixer, and mixing for 15min to obtain a mixture; and adding the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a screw cylinder is 180 ℃ in the first region, 200 ℃ in the second region, 210 ℃ in the third region, 200 ℃ in the fourth region, and the rotating speed of the double-screw extruder is 500r/min, so as to obtain the polypropylene composite material.

The hydroponic tank materials and the polypropylene composite materials obtained in examples and comparative examples were subjected to the performance tests shown in the following methods, and the results are shown in Table 1.

And (3) testing antibacterial performance: the antibacterial performance is tested according to the standard of QB/T2591-2003 'antibacterial plastic antibacterial performance test method and antibacterial effect' (detection bacteria: Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538);

testing the algae prevention performance: performing an algae prevention performance test according to GB/T24127-2009 Plastic algae resistance performance test method;

TABLE 1 test results of materials obtained in correspondence with examples 1 to 3 and comparative examples 1 to 2

As can be seen from the data in the table, the materials prepared in the examples have better antibacterial and mildewproof effects. The discoloration-preventing antibacterial algicide does not have any yellowing phenomenon in the process of processing a water culture tank material product or using the water culture tank material product, and always keeps transparent.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.