CN-121975143-A - Polypropylene composite material, modified antibacterial agent and preparation method thereof

CN121975143ACN 121975143 ACN121975143 ACN 121975143ACN-121975143-A

Abstract

The invention relates to the technical field of antibacterial agents and provides a polypropylene composite material, a modified antibacterial agent and a preparation method thereof, wherein the preparation method of the modified antibacterial agent comprises the steps of taking a carboxylic acid ligand and a soluble zinc salt with a molar ratio of (1-2) 1, dissolving the carboxylic acid ligand and the soluble zinc salt in DMF to prepare Zn-MOF, wherein the carboxylic acid ligand comprises a first active functional group, the first active functional group comprises at least one of amino, hydroxyl, mercapto and pyridine, activating the Zn-MOF in dilute hydrochloric acid, then placing the activated Zn-MOF in a silver nitrate solution with a first concentration for light shielding stirring, then placing the activated Zn-MOF in a silver nitrate solution with a second concentration for light shielding stirring to obtain activated Ag-MOF, wherein the first concentration is smaller than the second concentration, dispersing the activated Ag-MOF in the modifier for covalent bonding reaction, and the obtained modified antibacterial agent has better compatibility with resin so as to improve silver loading in the resin.

Inventors

CHANG XUESONG
BAO YI
BAI QING
DU JIANQIANG
Yi Xiaoliang
BIN LIMIN
SONG WEIJIAN
LIU ZHAOYANG
LI TAO
WANG JI

Assignees

海信家电集团股份有限公司
海信容声(广东)冰箱有限公司
海信冰箱有限公司

Dates

Publication Date: 20260505
Application Date: 20260327

Claims (10)

1. A preparation method of a modified antibacterial agent, which is characterized by comprising the following steps: Taking a carboxylic acid ligand and a soluble zinc salt with the molar ratio of (1-2) 1, and dissolving the carboxylic acid ligand and the soluble zinc salt in DMF to prepare and obtain Zn-MOF, wherein the carboxylic acid ligand comprises a first active functional group, and the first active functional group comprises at least one of amino, hydroxyl, mercapto and pyridine; Activating Zn-MOF in dilute hydrochloric acid, then placing the activated Zn-MOF in a silver nitrate solution with a first concentration, stirring in a dark place, and then placing the activated Zn-MOF in a silver nitrate solution with a second concentration, stirring in a dark place, so as to obtain activated Ag-MOF, wherein the first concentration is smaller than the second concentration; Dispersing the activated Ag-MOF in a modifier for covalent bonding reaction, washing and drying to obtain the modified antibacterial agent, wherein the modifier comprises a second active functional group, and the second active functional group comprises at least one of amino and carboxyl.
2. The method for producing a modified antibacterial agent according to claim 1, characterized in that, The carboxylic acid ligand comprises at least one of 5-hydroxy isophthalic acid, 2-amino terephthalic acid, 2, 6-pyridine dicarboxylic acid, 4-hydroxypyridine-2, 6-dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 2-methylimidazole-4, 5-dicarboxylic acid and mercaptosuccinic acid.
3. The method for producing a modified antibacterial agent according to claim 1, wherein the modifying agent is at least one of an aminosilane coupling agent and maleic anhydride.
4. The method for producing a modified antibacterial agent according to claim 3, characterized in that, The aminosilane coupling agent comprises at least one of aminosilanes such as gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyl diethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and the like.
5. The method for producing a modified antibacterial agent according to claim 1, characterized in that, The soluble zinc salt includes at least one of zinc nitrate, zinc acetate and zinc chloride.
6. The method for producing a modified antibacterial agent according to claim 1, characterized in that, The concentration range of the dilute hydrochloric acid is 0.05 mol/L-0.15 mol/L, and the activation time of the dilute hydrochloric acid is 1 h-3 h.
7. The method for producing a modified antibacterial agent according to claim 1, characterized in that, The range of the first concentration is 0.04mol/L to 0.06mol/L, the activated Zn-MOF is placed in the silver nitrate solution with the first concentration and stirred for 3h to 7h in a dark place, and/or And placing the activated Zn-MOF in a silver nitrate solution with the second concentration for 3-7 hours under dark stirring, wherein the second concentration range is 0.08-0.12 mol/L.
8. The method for producing a modified antibacterial agent according to claim 1, characterized in that, The reaction temperature of the carboxylic acid ligand and the soluble zinc salt dissolved in DMF is 120-160 ℃, the reaction time is 12-24 h, and/or The temperature range of the covalent bonding reaction is 40-80 ℃ and the reaction time range is 2-6 h.
9. A modified antibacterial agent, characterized in that the modified antibacterial agent is prepared by the preparation method of any one of claims 1 to 8.
10. The polypropylene composite material is characterized by comprising, by mass, 77% -88.15% of polypropylene, 0.1% -0.5% of the modified antibacterial agent according to claim 9, 10% -20% of a toughening agent, 0.3% -1% of an antioxidant, 0.1% -1% of a lubricant and 0.1% -0.5% of a degradation agent.

Description

Polypropylene composite material, modified antibacterial agent and preparation method thereof Technical Field The invention relates to the technical field of antibacterial agents, and mainly relates to a polypropylene composite material, a modified antibacterial agent and a preparation method thereof. Background The silver antibacterial agent has strong broad-spectrum antibacterial activity on microorganisms, has strong killing effect on various bacteria and even viruses, has high sterilization efficiency, and can be widely applied to the field of antibacterial plastics. The Metal Organic Framework (MOF) material has a porous structure and a high specific surface area, is an ideal silver ion carrier, and is used as a raw material for preparing the zinc-based MOF antibacterial agent more due to the advantages of low preparation cost, regular pore channel structure and the like. At present, the method for synthesizing the zinc-based MOF silver-loaded antibacterial agent mainly comprises a two-step preparation process of firstly synthesizing a carrier and then loading silver ions, but the problems of low silver loading amount, easiness in precipitation of silver ions, poor antibacterial durability, uneven distribution and weak binding force with ligands of the silver-based antibacterial agent, and poor compatibility with resin are easily caused, so that the mechanical properties of the material compounded by the antibacterial agent and the resin material are influenced. Disclosure of Invention The invention aims to provide a polypropylene composite material, a modified antibacterial agent and a preparation method thereof, which are used for improving the silver loading of a silver antibacterial agent in resin, reducing the difficult problem of poor antibacterial durability caused by precipitation amount and improving the compatibility of the silver antibacterial agent and the resin. In order to solve the problems, the invention provides a preparation method of a modified antibacterial agent, which comprises the following steps: Taking a carboxylic acid ligand and a soluble zinc salt with the molar ratio of (1-2) 1, and dissolving the carboxylic acid ligand and the soluble zinc salt in DMF to prepare and obtain Zn-MOF, wherein the carboxylic acid ligand comprises a first active functional group, and the first active functional group comprises at least one of amino, hydroxyl, mercapto and pyridine; Activating Zn-MOF in dilute hydrochloric acid, then placing the activated Zn-MOF in a silver nitrate solution with a first concentration, stirring in a dark place, and then placing the activated Zn-MOF in a silver nitrate solution with a second concentration, stirring in a dark place, so as to obtain activated Ag-MOF, wherein the first concentration is smaller than the second concentration; Dispersing the activated Ag-MOF in a modifier for covalent bonding reaction, washing and drying to obtain the modified antibacterial agent, wherein the modifier comprises a second active functional group, and the second active functional group comprises at least one of amino and carboxyl. In one embodiment, the carboxylic acid ligand comprises at least one of 5-hydroxyisophthalic acid, 2-amino terephthalic acid, 2, 6-pyridinedicarboxylic acid, 4-hydroxypyridine-2, 6-dicarboxylic acid, imidazole-4, 5-dicarboxylic acid, 2-methylimidazole-4, 5-dicarboxylic acid, and mercaptosuccinic acid. In one embodiment, the modifier is at least one of an aminosilane coupling agent and maleic anhydride. In one embodiment, the aminosilane coupling agent comprises at least one aminosilane such as gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyldiethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyl trimethoxysilane. In one embodiment, the soluble zinc salt comprises at least one of zinc nitrate, zinc acetate, and zinc chloride. In one embodiment, the concentration range of the dilute hydrochloric acid is 0.05 mol/L-0.15 mol/L, and the activation time of the dilute hydrochloric acid is 1 h-3 h. In one embodiment, the first concentration is in the range of 0.04mol/L to 0.06mol/L, and the activated Zn-MOF is placed in the silver nitrate solution with the first concentration and stirred for 3h to 7h in a dark place. In one embodiment, the second concentration range is 0.08 mol/L-0.12 mol/L, and the activated Zn-MOF is placed in the silver nitrate solution with the second concentration and stirred for 3-7 hours in a dark place. In one embodiment, the reaction temperature of the carboxylic acid ligand and the soluble zinc salt dissolved in DMF is 120-160 ℃ and the reaction time is 12-24 hours. In one embodiment, the temperature range of the covalent bonding reaction is 40-80 ℃ and the reaction time range is 2-6 hours. The second aspect of the invention provides a modified antibacterial agent, which is prepared by the preparation method of any embodiment. The third aspect of the inventio