CN109251359B - Functionalized hydrotalcite and application thereof in flame-retardant antibacterial polyamide master batch - Google Patents
Functionalized hydrotalcite and application thereof in flame-retardant antibacterial polyamide master batch Download PDFInfo
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Abstract
The invention discloses a functionalized hydrotalcite and application thereof in flame-retardant antibacterial polyamide master batches. The functionalized hydrotalcite is prepared by pretreating hydrotalcite with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and reacting the pretreated hydrotalcite with 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazine trione and guanyl urea phosphate for organic modification. Compared with the prior art, the functionalized hydrotalcite provided by the invention has good compatibility with polyamide resin when being applied to flame-retardant antibacterial polyamide master batches, so that the uniformity of the product is obviously improved, the functionalized hydrotalcite has the advantages of polyamide plastics in the prior art, most importantly, the antibacterial property of polyamide fibers can be obviously improved, the overall performance is excellent, plastic prepared products are protected from bacterial invasion, and the functionalized hydrotalcite has very important significance for application and further popularization of polyamide materials.
Description
Technical Field
The invention relates to a functionalized hydrotalcite and application thereof in flame-retardant antibacterial polyamide master batches.
Background
Polyamide (PA) is obtained by polycondensation of a dibasic acid and a diamine or an amino acid, and is a generic name of resins having a repeating amide group in a molecular chain. The polyamide can be prepared by ring-opening polymerization of lactam, or polycondensation of diamine and diacid. The DuPont company in the United states originally developed resins for fibers and was commercialized in 1939. In the 50 th of the 20 th century, injection molded products are developed and produced to replace metals to meet the requirements of light weight and cost reduction of downstream industrial products.
Polyamides can be classified into three groups according to their structures: aliphatic polyamides, aliphatic-aromatic polyamides, and aromatic polyamides. The aliphatic polyamide has many varieties, large yield and wide application, and the nomenclature of the polyamide is mainly determined by the specific carbon atom number of the synthetic monomer. The synthesis of polyamides can be mainly divided into three types: melt polycondensation, interfacial polycondensation, and solid phase polymerization.
Polyamides have good mechanical properties, heat resistance, abrasion resistance, chemical resistance, flame retardancy, and self-lubricity, are easy to process, have a low friction coefficient, and are widely used in the fields of electric and electronic parts, automobiles, furniture, building materials, films, and the like. There are generally two methods for modifying polyamides, one being modification by chemical means, such as copolymerization, grafting, crosslinking, etc.; the other is physical modification, which refers to a modification method in which no chemical change or only a very small degree of chemical reaction occurs in the whole modification process.
With the development and progress of society and the increasing living standard of materials, people have higher requirements on living and working environments, particularly sanitary environments. Because the plastic has the advantages of light weight, no corrosion, good insulation property and the like, the plastic is used in many links of household appliance production. However, in daily life, a considerable part of harmful bacteria are present and multiply on the surface of plastic products, such as: telephones, washing machines, computers, refrigerators, electric switches, etc., and cause various diseases by contact; therefore, in life, people inevitably come into contact with various microorganisms such as bacteria and mold and become a bacterial pollution source and a disease transmission source. But with the increasing awareness of people on health and environmental protection, the antibacterial and mildewproof effects are provided for household electric products which are frequently contacted in daily life.
Hydrotalcite (LDH for short) is a kind of anionic Layered Double Hydroxide (LDH), the thickness of its main body laminate is 0.48nm, and usually it is formed from 2 kinds of metal hydroxides, the laminate is positive electricity, and the longitudinal ordered arrangement forms three-dimensional crystal structure, and the equilibrium anions distributed between the laminates can be exchanged into organic anions with functionality, and the modification of organic anions can make the LDH layer spacing increase, and change from hydrophilicity to hydrophobicity. The organic modified LDH can also be peeled into two-dimensional nanosheets with high specific surface area and dispersed in a polymer matrix, so that multiple functions of flame retardance, wear resistance, optics, magnetism, electrical property and the like of the polymer are improved.
The functionalized hydrotalcite provided by the invention is organically modified and has good compatibility with polyamide resin, so that the product has good flame retardant and antibacterial properties.
Disclosure of Invention
Aiming at the requirements, the invention provides a functionalized hydrotalcite and an application thereof in flame-retardant antibacterial polyamide master batches.
Therefore, the invention provides the following technical scheme:
a functionalized hydrotalcite is prepared by the following method: adding hydrotalcite and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into water, stirring, mixing, reacting, filtering, washing a filter cake with distilled water, and drying an obtained product to obtain pretreated hydrotalcite; stirring, mixing and reacting the pretreated hydrotalcite, the 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione and water, filtering, and drying the obtained product to obtain the product.
In another technical scheme, the functionalized hydrotalcite is prepared by the following method: adding hydrotalcite and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into water, stirring, mixing, reacting, filtering, washing a filter cake with distilled water, and drying an obtained product to obtain pretreated hydrotalcite; stirring and mixing the pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water for reaction, filtering, and drying the obtained product to obtain the compound.
Preferably, the functionalized hydrotalcite is prepared by the following method: adding 90-110g of hydrotalcite and 20-40g of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane into 950-1050mL of water, stirring for 2-4h at 40-60 ℃ at the rotating speed of 200-400r/min, filtering by using 500-mesh filter cloth, washing a filter cake for 2-4 times by using distilled water, and drying the obtained product for 20-40h at 40-60 ℃ to obtain pre-treated hydrotalcite; mixing the pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazine trione, guanylurea phosphate and water, stirring and reacting at 40-60 ℃ at the rotating speed of 200-400r/min for 3-5h, filtering by using 500-mesh filter cloth with 800 meshes, and drying the obtained product at 40-60 ℃ for 20-40h to obtain the guanylurea phosphate.
Preferably, the mass ratio of the pretreated hydrotalcite to the 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione to the guanylurea phosphate to the water is 1: (0.1-0.3): (0.05-0.2): (8-12).
The invention also discloses application of the functionalized hydrotalcite in flame-retardant antibacterial polyamide master batches.
The concrete application is as follows:
the flame-retardant antibacterial polyamide master batch comprises the following raw materials in parts by weight: 80-90 parts of polyamide, 2-5 parts of silane coupling agent, 1-2 parts of maleic anhydride grafted compatilizer, 15-25 parts of functionalized hydrotalcite as claimed in any one of claims 1-4, 1-2 parts of antioxidant, 1-2 parts of N, N' -ethylene bis stearamide and 1-2 parts of antibacterial additive; weighing the raw materials according to the parts by weight, stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 400-800r/min for 15-20min, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling and grain cutting to obtain the flame-retardant antibacterial polyamide master batch. The temperature of the first area of the double-screw extruder is 170-185 ℃, the temperature of the second area is 225-245 ℃, the temperature of the third area is 255-275 ℃ and the temperature of the fourth area is 250-270 ℃; the fifth zone is 230 ℃ and 250 ℃, the retention time is 1-2 minutes, and the pressure is 10-15 Mpa.
The polyamide is PA6 or PA 66; the silane coupling agent is 3-chloropropylmethyldimethoxysilane or 3- (2, 3-glycidoxy) propyltrimethoxysilane; the maleic anhydride grafted compatilizer is maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene or maleic anhydride grafted EPDM; the antioxidant is triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate.
The antibacterial additive is at least one of a quaternary phosphonium salt type halamine antibacterial agent and (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride. Further, the antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, a (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: (0.4-0.6).
The invention has the beneficial effects that:
the invention prepares a functional hydrotalcite by modifying common hydrotalcite, and the functional hydrotalcite is applied to flame-retardant antibacterial polyamide master batches and has good compatibility with polyamide resin, so that the uniformity of the product is obviously improved, the functional hydrotalcite not only has the advantages of polyamide plastics in the prior art, but also can obviously improve the antibacterial performance of polyamide fibers, has excellent overall performance, protects plastic prepared products from bacterial invasion, and has very important significance for the application and further popularization of polyamide materials.
Detailed Description
The materials used are described below: the quaternary phosphonium salt type halamine antibacterial agent was prepared as shown in example 1 of chinese patent application No. 201510249967.8. (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethylammonium chloride was prepared according to the method shown in example 3 of the chinese patent application No. 201210295496.0. N, N' -ethylene bis stearamide, CAS No.: 110-30-5. Diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, CAS number: 976-56-7. 3-chloropropylmethyldimethoxysilane, CAS number: 18171-19-2. Maleic anhydride grafted EPDM was supplied by Catalph plastics Mill, Dongyuan county, model 9905E. Hydrotalcite is provided by Jingjiang city Kanggao Special plastics science and technology Limited, and has a model of FM300 and a granularity of 300 meshes. 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione was prepared according to the method shown in example 3 of the Chinese patent application No. 201210362485. X. 3- (2, 3-glycidoxy) propyltrimethoxysilane, CAS no: 2530-83-8. Guanylurea phosphate was manufactured by Zhengzhou Guanda chemical products Co., Ltd., model number 2203. PA6 is supplied by DuPont, USA, and is 73G 20L.
Example 1
The production process of the flame-retardant antibacterial polyamide master batch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture through an air duct, and performing hot cutting on the mixture into cylindrical particles with the diameter of 3 multiplied by 3mm through a cutter, wherein the temperature of a first area of the double-screw extruder is 175 ℃, the temperature of a second area of the double-screw extruder is 235 ℃, the temperature of a third area of the double-screw extruder is 270 ℃, the temperature of a fourth area of the double-screw extruder is 260 ℃, the temperature of a fifth area of the double-screw extruder is 240 ℃, the residence time.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 2
The production process of the flame-retardant antibacterial polyamide master batch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture through an air duct, and performing hot cutting on the mixture into cylindrical particles with the diameter of 3 multiplied by 3mm through a cutter, wherein the temperature of a first area of the double-screw extruder is 175 ℃, the temperature of a second area of the double-screw extruder is 235 ℃, the temperature of a third area of the double-screw extruder is 270 ℃, the temperature of a fourth area of the double-screw extruder is 260 ℃, the temperature of a fifth area of the double-screw extruder is 240 ℃, the residence time.
The filler is hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 3
The production process of the flame-retardant antibacterial polyamide master batch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture through an air duct, and performing hot cutting on the mixture into cylindrical particles with the diameter of 3 multiplied by 3mm through a cutter, wherein the temperature of a first area of the double-screw extruder is 175 ℃, the temperature of a second area of the double-screw extruder is 235 ℃, the temperature of a third area of the double-screw extruder is 270 ℃, the temperature of a fourth area of the double-screw extruder is 260 ℃, the temperature of a fifth area of the double-screw extruder is 240 ℃, the residence time.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment of hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazine trione and water are mixed according to the mass ratio of 1: 0.2: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent.
Example 4
The production process of the flame-retardant antibacterial polyamide master batch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture through an air duct, and performing hot cutting on the mixture into cylindrical particles with the diameter of 3 multiplied by 3mm through a cutter, wherein the temperature of a first area of the double-screw extruder is 175 ℃, the temperature of a second area of the double-screw extruder is 235 ℃, the temperature of a third area of the double-screw extruder is 270 ℃, the temperature of a fourth area of the double-screw extruder is 260 ℃, the temperature of a fifth area of the double-screw extruder is 240 ℃, the residence time.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride.
Example 5
The production process of the flame-retardant antibacterial polyamide master batch comprises the following steps:
(1) weighing the following raw materials in parts by weight: PA 685 parts, 3 parts of 3-chloropropylmethyl dimethoxy silane, 1.5 parts of maleic anhydride grafted EPDM (ethylene-propylene-diene monomer), 20 parts of filler, 1.5 parts of diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphate, 1.5 parts of N, N' -ethylene bis stearamide and 1.5 parts of antibacterial additive;
(2) stirring and mixing the raw materials in a high-speed mixer at the rotating speed of 600r/min for 16min, adding the mixture into a double-screw extruder, performing melt extrusion, cooling the mixture through an air duct, and performing hot cutting on the mixture into cylindrical particles with the diameter of 3 multiplied by 3mm through a cutter, wherein the temperature of a first area of the double-screw extruder is 175 ℃, the temperature of a second area of the double-screw extruder is 235 ℃, the temperature of a third area of the double-screw extruder is 270 ℃, the temperature of a fourth area of the double-screw extruder is 260 ℃, the temperature of a fifth area of the double-screw extruder is 240 ℃, the residence time.
The filler is functionalized hydrotalcite.
The preparation method of the functionalized hydrotalcite comprises the following steps: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of deionized water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, wherein the mass ratio of the filter cake to the water after each washing is 1: 2, drying the obtained product at the temperature of 50 ℃ for 30h to obtain pretreated hydrotalcite; the pretreatment method comprises the following steps of (1) preparing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione, guanylurea phosphate and water according to the mass ratio of 1: 0.2: 0.08: 10, stirring and reacting for 4 hours at the rotation speed of 300r/min at the temperature of 50 ℃, filtering by using 600-mesh filter cloth, and drying the obtained product for 30 hours at the temperature of 50 ℃ to obtain the functionalized hydrotalcite.
The antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: 0.5 of a mixture.
Test example 1
The flame-retardant antibacterial polyamide master batches of examples 1 to 5 were subjected to a performance test. Specific results are shown in table 1.
And (3) testing antibacterial performance: the bacterial strain is tested according to the national common people's republic of China light industry Standard QB/T2591-: staphylococcus aureus (ATCC 6538).
And (3) oxygen index test: according to the standard GB/T2406.1-2008.
And (3) low temperature resistance test: placing the flame-retardant antibacterial polyamide master batch at 25 ℃ for 48 hours, and then carrying out tensile strength (the value is marked as A)1) The test was carried out, and the tensile strength (value A) was measured after leaving at-15 ℃ for 48 hours2) Testing, wherein the tensile strength is tested according to the standard GB/T1040.1-2006. The tensile strength decrease rate was calculated as follows. Tensile strength reduction (%) - (A)1-A2)/A1×100。
Table 1: test result table
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.
Claims (3)
1. The functionalized hydrotalcite is characterized by being prepared by the following method: adding 100g of hydrotalcite and 24g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into 1000mL of water, stirring for 3h at 50 ℃ at the rotating speed of 300r/min, filtering by adopting 600-mesh filter cloth, washing a filter cake for 3 times by using distilled water, and drying the obtained product for 30h at 50 ℃ to obtain pre-treated hydrotalcite; mixing pretreated hydrotalcite, 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazine trione, guanylurea phosphate and water, stirring and reacting at 50 ℃ at the rotating speed of 300r/min for 4 hours, filtering by using 600-mesh filter cloth, and drying the obtained product at 50 ℃ for 30 hours to obtain the compound; the mass ratio of the pretreated hydrotalcite to the 1-chloro-3-hydroxymethyl-5-epoxypropyl-S-triazinetrione to the guanylurea phosphate to the water is 1: 0.2: 0.08: 10.
2. the use of the functionalized hydrotalcite of claim 1 in flame retardant antibacterial polyamide masterbatch.
3. The use of the functionalized hydrotalcite of claim 2 in flame retardant and antibacterial polyamide masterbatch, wherein the flame retardant and antibacterial polyamide masterbatch comprises the following raw materials in parts by weight: 80-90 parts of polyamide, 2-5 parts of silane coupling agent, 1-2 parts of maleic anhydride grafted compatilizer, 15-25 parts of functionalized hydrotalcite as defined in claim 1, 1-2 parts of antioxidant, 1-2 parts of N, N' -ethylene bis stearamide and 1-2 parts of antibacterial additive; the polyamide is PA6 or PA 66; the silane coupling agent is 3-chloropropylmethyldimethoxysilane or 3- (2, 3-glycidoxy) propyltrimethoxysilane; the maleic anhydride grafted compatilizer is maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene or maleic anhydride grafted EPDM; the antioxidant is triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate; the antibacterial additive is a quaternary phosphonium salt type halamine antibacterial agent, (3-chloro-2-hydroxypropyl) - (5, 5-dimethylhydantoin-1) methyl-dimethyl ammonium chloride according to a mass ratio of 1: (0.4-0.6).
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| CN112876880B (en) * | 2021-01-18 | 2022-05-03 | 浙江嘉澳环保科技股份有限公司 | Preparation method and product of modified hydrotalcite |
| CN113477085B (en) * | 2021-07-08 | 2022-09-02 | 自然资源部天津海水淡化与综合利用研究所 | Polyamide composite reverse osmosis membrane with high permselectivity and antibacterial property and preparation method thereof |
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