阅读说明：本技术 一种无机-多种有机复合抗菌剂的制备方法和应用 (Preparation method and application of inorganic-multiple organic composite antibacterial agent ) 是由 施燕琴 王旭 杨蝶霜 鲁淞彦 沈嘉琪 陈思 马猛 何荟文 于 2019-11-25 设计创作，主要内容包括：本发明涉及抗菌剂领域,尤其涉及一种无机-多种有机复合抗菌剂的制备方法和应用。所述制备方法包括：将醛类抗菌剂通过偶联剂接枝到无机抗菌剂上,得到无机-单种有机复合抗菌剂,进一步将溴化酚类抗菌剂接枝到无机-单种有机复合抗菌剂上,得到无机-多种有机复合抗菌剂；所述无机-多种有机复合抗菌剂用于抗菌PP复合材料的制备。本发明制备方法简洁高效,能够高效制备得到无机-多种有机复合抗菌剂；所得无机-多种有机复合抗菌剂在具备良好的常规抗菌性能同时,还具有良好的抗黑曲霉能力,抗菌作用对象更广,效果更优；所得无机-多种有机复合抗菌剂具有良好的耐迁移性,制备和使用过程更加环保；在较低用量的情况下即可实现良好的抗菌效果。(The invention relates to the field of antibacterial agents, in particular to a preparation method and application of an inorganic-multiple organic composite antibacterial agent. The preparation method comprises the following steps: grafting the aldehyde antibacterial agent onto the inorganic antibacterial agent through a coupling agent to obtain an inorganic-single organic composite antibacterial agent, and further grafting the brominated phenol antibacterial agent onto the inorganic-single organic composite antibacterial agent to obtain an inorganic-multiple organic composite antibacterial agent; the inorganic-multiple organic composite antibacterial agent is used for preparing the antibacterial PP composite material. The preparation method is simple and efficient, and can be used for efficiently preparing inorganic-multiple organic composite antibacterial agents; the obtained inorganic-multiple organic composite antibacterial agent has good conventional antibacterial performance, and also has good Aspergillus niger resistance, wider antibacterial action object and better effect; the obtained inorganic-multiple organic composite antibacterial agent has good migration resistance, and the preparation and use processes are more environment-friendly; can realize good antibacterial effect under the condition of lower dosage.)

1. A method for preparing inorganic-multiple organic composite antibacterial agent is characterized in that,

the preparation method comprises the following steps:

the aldehyde antibacterial agent is grafted to the inorganic antibacterial agent through a coupling agent to obtain an inorganic-single organic composite antibacterial agent, and the brominated phenol antibacterial agent is further grafted to the inorganic-single organic composite antibacterial agent to obtain the inorganic-multiple organic composite antibacterial agent.

2. The method for preparing an inorganic-multiple organic composite antibacterial agent according to claim 1,

the preparation method specifically comprises the following steps:

1) modification of inorganic antibacterial agent: dissolving a coupling agent in a solvent to prepare a coupling agent solution, placing an inorganic antibacterial agent in the coupling agent solution for modification treatment, filtering, cleaning and drying to obtain a modified inorganic antibacterial agent;

2) preparation of inorganic-single organic composite antibacterial agent: adding an aldehyde antibacterial agent into a modified inorganic antibacterial agent dispersion solution solvent, grafting through a first chemical reaction, filtering, cleaning and drying to obtain an inorganic-single organic composite antibacterial agent;

3) preparing inorganic-multiple organic composite antibacterial agents: dispersing the inorganic-single organic composite antibacterial agent in a solvent, adding a brominated phenol antibacterial agent, carrying out secondary reaction grafting, and then filtering, cleaning and drying to obtain the inorganic-multiple organic composite antibacterial agent.

3. The method for producing an inorganic-multiple organic composite antibacterial agent according to claim 2,

the mass ratio of the coupling agent used in the step 1) to the inorganic antibacterial agent is (0.5-10): (90-99.5);

the coupling agent is a coupling agent containing amino.

4. The method for producing an inorganic-multiple organic composite antibacterial agent according to claim 2 or 3,

step 1) the modification treatment comprises the following steps: mixing at 600-1200 rpm for 10-30 min;

the solvent in the step 1) is an alcohol-water mixture, and the volume ratio of alcohol to water in the alcohol-water mixture is (1-9): 1;

the particle size of the inorganic antibacterial agent in the step 1) is 10-100 nm.

5. The method for producing an inorganic-multiple organic composite antibacterial agent according to claim 2,

the dosage mass ratio of the modified inorganic antibacterial agent to the aldehyde antibacterial agent in the step 2) is (90-97): (3-10);

the first chemical reaction grafting comprises the following steps: mixing and standing for 3-5 h.

6. The method for producing an inorganic-multiple organic composite antibacterial agent according to claim 2,

the mass ratio of the inorganic-single organic composite antibacterial agent to the brominated phenol antibacterial agent used in the step 3) is (93-99): (1-7);

the second reactive grafting is as follows: reacting for 4-6 h at 40-60 ℃.

7. The method for producing an inorganic-multiple organic composite antibacterial agent according to claim 1, 2 or 6,

the brominated phenol antibacterial agent is an antibacterial agent containing phenolic hydroxyl and terminal bromo;

the brominated phenol antibacterial agent is prepared by dissolving a phenol antibacterial agent in a solvent, adding an initiator and a brominating agent, reacting for 4-6 h at 40-60 ℃, and distilling at 45-55 ℃.

8. Use of the inorganic-organic complex antibacterial agent obtained by the method according to any one of claims 1 to 7,

the inorganic-multiple organic composite antibacterial agent is used for preparing the antibacterial PP composite material.

9. The use of an inorganic-multiple organic composite antibacterial agent according to claim 8,

the preparation method of the antibacterial PP composite material comprises the following steps:

the method comprises the steps of taking inorganic-multiple organic composite antibacterial agents, antioxidants and PP base materials as raw materials, carrying out melt blending and extrusion, wherein the extrusion temperature is 170-190 ℃, the feeding speed is 35-45 r/min, and the screw rotating speed is 45-55 rpm, so that the antibacterial PP composite material is obtained.

10. The use of an inorganic-organic composite antibacterial agent according to claim 9,

the inorganic-multiple organic composite antibacterial agent accounts for 1-10 wt% of the total mass of the raw materials;

the antioxidant accounts for 1-2 wt% of the total mass of the raw materials.

Technical Field

The invention relates to the field of antibacterial agents, in particular to a preparation method and application of an inorganic-multiple organic composite antibacterial agent.

Background

Pathogenic microorganisms such as bacteria are one of the important factors harming human health, and the antibacterial polymer products have become an important research direction for polymer materials because the polymer products contain long carbon chain structures and small molecular additives and the surfaces of the polymer products are easy to grow bacteria. Because the inorganic antibacterial agent has the characteristics of low antibacterial efficiency and safety and environmental protection, and the organic antibacterial agent has the characteristics of high antibacterial efficiency and easy migration, the research hotspot of compounding the inorganic antibacterial agent and the organic antibacterial agent into the antibacterial agent for the current high polymer material is provided.

The composite antibacterial agent is generally prepared by compounding two or more than two antibacterial agents by means of physical blending or chemical reaction. For example, Zhang Wei (Zhang Wei, Jiang Gong, Zhang Meiying. antibacterial PP plastics and preparation method thereof [ P ].2013-09-11 ], and the like, chitin, nano zinc oxide, nano nickel powder and nano silver oxide are simply and physically blended and then are melted and blended with a PP matrix to prepare the antibacterial PP plastics, and the antibacterial rate of the antibacterial PP plastics is over 90 percent. Elsholtzia essential oil antibacterial soap and a preparation method thereof [ P ].2018-12-14 ], and the like, coconut oil, aromatherapy essential oil and other natural antibacterial agents are physically blended to prepare the compound antibacterial agent. The antibacterial performance of the antibacterial composition is tested by an antibacterial zone test, and the antibacterial zones for escherichia coli and staphylococcus aureus reach 7.5mm and 11mm respectively. However, the disadvantages of single antibacterial agents, such as low antibacterial efficiency of some inorganic antibacterial agents, easy generation of bacterial resistance by organic antibacterial agents, easy migration, etc., cannot be completely overcome by simple physical blending. Compared with the organic antibacterial agent with an artificially synthesized structure, the inorganic antibacterial agent and the organic antibacterial agent with a natural structure are safer and more environment-friendly, so that the inorganic-organic composite antibacterial agent which is safe and environment-friendly is prepared by the inorganic antibacterial agent and the organic antibacterial agent with a natural structure through a chemical grafting method, and the method is an effective method for preparing the antibacterial agent with high antibacterial rate and low migration.

Each of the natural organic antibacterial agents has different antibacterial effects on different species, for example, the hydrophilic antibacterial agent has a higher antibacterial efficiency against Escherichia coli and the lipophilic antibacterial agent has a higher antibacterial efficiency against Staphylococcus aureus, and there is a significant synergistic antibacterial effect between the different natural antibacterial agents according to the literature, for example, Dorman et al [ DORMAN H J D, DEANS SG. antimicrobial agents from plants: antibacterial activity of plants volatile oils [ J ]. Journal of Applied Microbiology,2010,88(2):308-16 ] report that oregano and thyme essential oils have a synergistic antibacterial effect against Escherichia coli, Nayanathara et al [ NAYANATHARA K H G, RATNASEKERAD.Efficacy of cina and citrus oils in the control of microorganisms, L. in bulk stored grain J.: Journal of cinnamic aldehyde, 201, cinnamon aldehyde, 201, and cinnamon aldehyde, which have been studied as the main antibacterial effects.

That is, the current research shows that part of natural organic antibacterial agents can generate good synergistic antibacterial effect by compounding.

Disclosure of Invention

The invention provides a preparation method and application of an inorganic-multiple organic composite antibacterial agent, aiming at solving the problems that the existing chemically modified inorganic-single organic composite antibacterial agent can not realize comprehensive antibacterial and the antibacterial efficiency of the composite antibacterial agent is further improved. The invention aims to: firstly, providing a chemical preparation method of an inorganic-multiple organic composite antibacterial agent; secondly, a plurality of proper organic antibacterial agents are selected for compounding, so that the plurality of organic antibacterial agents generate a synergistic effect and the antibacterial capacity is improved; thirdly, the obtained composite antibacterial agent has good spectrum sterilization effect by the composite use of a plurality of organic antibacterial agents, and can kill and inhibit a plurality of bacteria; fourthly, the composite antibacterial agent has good migration resistance and is safer and more environment-friendly; fifthly, excellent antibacterial property can be generated under the condition of extremely low dosage; sixthly, the method can be used for preparing various plastic matrix composite materials such as PP and the like.

In order to achieve the purpose, the invention adopts the following technical scheme.

A method for preparing inorganic-multiple organic composite antibacterial agent,

the preparation method comprises the following steps:

the aldehyde antibacterial agent is grafted to the inorganic antibacterial agent through a coupling agent to obtain an inorganic-single organic composite antibacterial agent, and the brominated phenol antibacterial agent is further grafted to the inorganic-single organic composite antibacterial agent to obtain the inorganic-multiple organic composite antibacterial agent.

The inorganic antibacterial agent comprises one or more of inorganic antibacterial agents such as zinc oxide, titanium dioxide, silicon dioxide, zeolite antibacterial agents and the like, the coupling agent is a coupling agent containing at least one amino group and comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldioxysilane, 3-aminopropyltrimethoxysilane and isopropyl tri (n-ethylamino) titanate, and the brominated phenolic antibacterial agent contains bromine and phenolic hydroxyl. In the modification process, firstly, hydroxyl on the surface of the inorganic antibacterial agent reacts with hydroxyl in the hydrolyzed coupling agent, and the coupling agent is grafted to the surface of the inorganic antibacterial agent to prepare the modified inorganic antibacterial agent; secondly, amino contained in the modified inorganic antibacterial agent and aldehyde contained in the aldehyde antibacterial agent are used for Schiff base reaction, namely, a bridge which is compositely grafted with the aldehyde antibacterial agent is formed through modification treatment of a coupling agent, and the aldehyde antibacterial agent and the inorganic antibacterial agent are composited. The addition amount of the aldehyde antibacterial agent is controlled to ensure that the inorganic antibacterial agent retains a certain amount of unreacted amino groups so as to carry out the subsequent secondary chemical reaction grafting. And finally, when the brominated phenolic antibacterial agent is further grafted, the bromine group and the unreacted amino group on the modified inorganic antibacterial agent further perform chemical reaction, so that the second organic antibacterial agent-brominated phenolic antibacterial agent is grafted on the surface of the inorganic antibacterial agent, and the inorganic-multiple organic composite antibacterial agent grafted with multiple organic antibacterial agents is prepared.

As a preference, the first and second liquid crystal compositions are,

the preparation method specifically comprises the following steps:

1) modification of inorganic antibacterial agent: dissolving a coupling agent in a solvent to prepare a coupling agent solution, placing an inorganic antibacterial agent in the coupling agent solution for modification treatment, filtering, cleaning and drying to obtain a modified inorganic antibacterial agent;

2) preparation of inorganic-single organic composite antibacterial agent: adding an aldehyde antibacterial agent into a modified inorganic antibacterial agent dispersion solution solvent, grafting through a first chemical reaction, filtering, cleaning and drying to obtain an inorganic-single organic composite antibacterial agent;

3) preparing inorganic-multiple organic composite antibacterial agents: dispersing the inorganic-single organic composite antibacterial agent in a solvent, adding a brominated phenol antibacterial agent, carrying out secondary reaction grafting, and then filtering, cleaning and drying to obtain the inorganic-multiple organic composite antibacterial agent.

The specific procedures are illustrated by taking zinc oxide (ZnO, inorganic antibacterial agent), 3-aminopropyltriethoxysilane (KH550, coupling agent containing amino group), cinnamaldehyde (CA, aldehyde antibacterial agent, natural organic antibacterial agent) and brominated thymol (THY-Br, brominated phenol antibacterial agent, natural organic antibacterial agent) as examples. The specific routes of the above components are shown in FIGS. 1 to 3.

FIG. 1 shows that ZnO and KH550 are subjected to activation reaction at room temperature, the inorganic antibacterial agent ZnO rich in active hydroxyl is subjected to chemical reaction with hydroxyl generated after hydrolysis of the coupling agent in a solvent to form modified inorganic antibacterial agent O-ZnO, and amino groups on the original coupling agent in the modified inorganic antibacterial agent O-ZnO in FIG. 2 and aldehyde groups in CA are subjected to generation of a matPerforming Schiff base reaction to obtain inorganic-single organic composite antibacterial agent O-ZnO-CA, reacting unreacted amino on the surface of modified inorganic antibacterial agent O-ZnO in inorganic-single organic composite antibacterial agent O-ZnO-CA in figure 3 with bromine on brominated phenol antibacterial agent THY-Br, removing hydrogen bromide to obtain final product inorganic-multiple organic composite antibacterial agent O-ZnO-C₂T₂. In the process, actually, a large amount of KH550 is grafted on the ZnO surface in the process of activating and modifying in the process shown in figure 1, and the grafting amount of the aldehyde antibacterial agent on the O-ZnO surface is controlled by controlling the feeding amount, so that the O-ZnO contains surplus unreacted amino for carrying out chemical reaction with a second natural organic antibacterial agent THY-Br, and further, THY is grafted, thereby forming the inorganic-multiple organic composite antibacterial agent. This kind of grafting mode makes two kinds of antibacterial agents interdispersion, even grafting on inorganic antibacterial agent surface, and the maximize exerts the collaborative antibacterial effect between the different natural organic antibacterial agents, possesses more diversified antibacterial effect, can play good antibiotic, bactericidal effect to all kinds of fungus homoenergetic to stable in structure has good migration resistance, and because antibiotic efficient, can realize good antibacterial effect under the extremely low quantity condition.

As a preference, the first and second liquid crystal compositions are,

the mass ratio of the coupling agent used in the step 1) to the inorganic antibacterial agent is (0.5-10): (90-99.5);

the coupling agent is a coupling agent containing amino.

The use amount of the coupling agent determines the grafting amount of the organic antibacterial agent, and a large number of research experiments show that the aldehyde antibacterial agent and the brominated phenol antibacterial agent can be grafted better by controlling the use amount ratio of the coupling agent to the inorganic antibacterial agent to be the ratio. The coupling agent containing amino is more favorable for the combination of the modified inorganic antibacterial agent, the aldehyde antibacterial agent and the brominated phenol antibacterial agent.

As a preference, the first and second liquid crystal compositions are,

step 1) the modification treatment comprises the following steps: mixing at 600-1200 rpm for 10-30 min;

the solvent in the step 1) is an alcohol-water mixture, and the volume ratio of alcohol to water in the alcohol-water mixture is (1-9): 1;

the particle size of the inorganic antibacterial agent in the step 1) is 10-100 nm.

The modification treatment operation is simple, and only stirring and mixing are needed. The alcohol-water mixture is used as the solvent because the silane coupling agent is easy to hydrolyze in water, and the ethanol can play a role in dissolving and ensuring the stability of the hydrolyzed solution of the silane coupling agent, thereby being beneficial to the modification of the inorganic antibacterial agent by the silane coupling agent.

As a preference, the first and second liquid crystal compositions are,

the dosage mass ratio of the modified inorganic antibacterial agent to the aldehyde antibacterial agent in the step 2) is (90-95): (5-10);

the first chemical reaction grafting comprises the following steps: mixing and standing for 3-5 h.

The above amount is superior to the grafting effect. The grafting process of the first chemical reaction can be heated at a lower temperature, such as 40-60 ℃, so that the forward promotion of the reaction is facilitated, the reaction efficiency is improved,

As a preference, the first and second liquid crystal compositions are,

the mass ratio of the inorganic-single organic composite antibacterial agent to the brominated phenol antibacterial agent in the step 3) is (90-95): (5-10); the second reactive grafting is as follows: reacting for 4-6 h at 40-60 ℃.

The above amount is superior to the grafting effect. In the second reaction grafting process, because the reactivity of the brominated phenolic antibacterial agent and the amino group is lower than that of the first reaction, heating at a lower temperature is required to promote the reaction process so as to improve the reaction effect and reduce the grafting difficulty of the brominated phenolic antibacterial agent, and the problem that the solvent is easy to volatilize quickly and the like is caused when the heating temperature is too high.

As a preference, the first and second liquid crystal compositions are,

the brominated phenol antibacterial agent is an antibacterial agent containing phenolic hydroxyl and terminal bromo;

the brominated phenol antibacterial agent is prepared by dissolving a phenol antibacterial agent in a solvent, adding an initiator and a brominating agent, reacting for 4-6 h at 40-60 ℃, and distilling at 45-55 ℃.

The formation process of brominated phenolic antibacterial agent comprises phenolic antibacterial agent Thymol (THY) and cupric bromide (CuBr)₂) For example, its concrete structureThe synthesis process is shown in fig. 4, under the action of dibenzoyl peroxide initiator (BPO), bromide ions formed by dissolving copper bromide in solvent displace the hydrogen radical on thymol, so as to bromize the phenolic antibacterial agent, and obtain brominated thymol (THY-Br). The process needs heating at a lower temperature to promote the reaction to start and continue to be carried out positively, and the subsequent distillation can effectively separate the product to obtain the high-purity brominated phenol antibacterial agent (THY-Br).

An application of inorganic-multiple organic composite antibacterial agent,

the inorganic-multiple organic composite antibacterial agent is used for preparing the antibacterial PP composite material.

When the inorganic-multiple organic composite antibacterial agent prepared by the invention is used in an antibacterial PP composite material, extremely excellent antibacterial effect can be achieved with extremely low dosage.

As a preference, the first and second liquid crystal compositions are,

the preparation method of the antibacterial PP composite material comprises the following steps:

the method comprises the steps of taking inorganic-multiple organic composite antibacterial agents, antioxidants and PP base materials as raw materials, carrying out melt blending and extrusion, wherein the extrusion temperature is 170-190 ℃, the feeding speed is 35-45 r/min, and the screw rotating speed is 45-55 rpm, so that the antibacterial PP composite material is obtained.

The preparation method is simple and efficient, and the antibacterial PP composite material can be efficiently prepared.

As a preference, the first and second liquid crystal compositions are,

the inorganic-multiple organic composite antibacterial agent accounts for 1-10 wt% of the total mass of the raw materials;

the antioxidant accounts for 1-2 wt% of the total mass of the raw materials.

The actual dosage of the inorganic-multiple organic composite antibacterial agent can be maintained at 1-2 wt%, and the excellent antibacterial effect can be realized. The addition of the antioxidant is beneficial to delaying the aging of the PP material.

The invention has the beneficial effects that:

1) the preparation method is simple and efficient, and the inorganic-multiple organic composite antibacterial agent can be efficiently prepared;

2) the obtained inorganic-multiple organic composite antibacterial agent has good conventional antibacterial performance, and further has good Aspergillus niger resistance, wider antibacterial action object and better effect;

3) the obtained inorganic-multiple organic composite antibacterial agent has good migration resistance, and the preparation and use processes are more environment-friendly;

4) can realize good antibacterial effect under the condition of lower dosage.

Drawings

FIG. 1 is a schematic view of the modification process of the inorganic antibacterial agent of step 1);

FIG. 2 is a schematic view showing the preparation of the inorganic-single organic composite antibacterial agent of step 2);

FIG. 3 is a schematic view showing the preparation of the inorganic-multiple organic composite antibacterial agent of step 3);

FIG. 4 is a schematic of the preparation of brominated phenolic antibacterial agents.

Detailed Description

The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.

Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.