阅读说明：本技术 一种荧光抗菌高分子材料及其制备方法和应用 (Fluorescent antibacterial high polymer material and preparation method and application thereof ) 是由 乔金樑 胡晨曦 张晓红 茹越 宋志海 郭照琰 蔡传伦 赖金梅 戚桂村 蒋海斌 高 于 2019-04-08 设计创作，主要内容包括：本发明涉及高分子材料领域的一种荧光抗菌高分子材料和其制备方法及用途。所述荧光抗菌高分子材料包括马来酸酐共聚物锌盐衍生物,激发波长为330～430nm,其最强荧光发射位于400～550nm。所述马来酸酐共聚物锌盐衍生物为羧酸基团上结合有锌离子的马来酸酐共聚物。所述荧光抗菌高分子材料对大肠杆菌、金黄葡萄球菌的抗菌率均大于99％。本发明的荧光抗菌高分子材料是将马来酸酐共聚物加入到碱金属氢氧化物的水溶液中充分反应后加入锌盐和/或锌盐水溶液充分反应生成而得。本发明的荧光抗菌高分子材料所涉及原料及工艺中所使用物品价格低廉,制备方法简单且环境污染低,且所述荧光抗菌高分子材料的荧光性能优异、安全性高、抗菌效果持久,适于工业化应用。(The invention relates to a fluorescent antibacterial high polymer material in the field of high polymer materials, and a preparation method and application thereof. The fluorescent antibacterial high polymer material comprises a maleic anhydride copolymer zinc salt derivative, the excitation wavelength is 330-430 nm, and the strongest fluorescence emission is 400-550 nm. The zinc salt derivative of the maleic anhydride copolymer is a maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups. The antibacterial rate of the fluorescent antibacterial high polymer material to escherichia coli and staphylococcus aureus is more than 99%. The fluorescent antibacterial high polymer material is prepared by adding a maleic anhydride copolymer into an aqueous solution of alkali metal hydroxide for full reaction, and then adding zinc salt and/or a zinc salt aqueous solution for full reaction. The fluorescent antibacterial high polymer material has the advantages of low price of raw materials and articles used in the process, simple preparation method, low environmental pollution, excellent fluorescence performance, high safety and lasting antibacterial effect, and is suitable for industrial application.)

1. A fluorescent antibacterial high-molecular material comprises a zinc salt derivative of a maleic anhydride copolymer, wherein the zinc salt derivative of the maleic anhydride copolymer is a maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups.

2. The fluorescent antibacterial polymer material according to claim 1, characterized in that:

the maleic anhydride copolymer is maleic anhydride alternating copolymer and comprises at least one of maleic anhydride linear alternating copolymer and maleic anhydride cross-linked alternating copolymer.

3. The fluorescent antibacterial polymer material according to claim 2, characterized in that:

the maleic anhydride alternating copolymer is at least one of alternating copolymers obtained by copolymerizing maleic anhydride and monomers containing isolated carbon-carbon double bonds; preferably maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinylpyrrolidone alternating copolymer, maleic anhydride-itaconic acid alternating copolymer; more preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.

4. The fluorescent antibacterial polymer material according to claim 1, characterized in that:

the weight fraction of the zinc element in the maleic anhydride copolymer zinc salt derivative is 10-70%, preferably 20-60%.

5. The fluorescent antibacterial polymer material according to claim 1, characterized in that:

divalent zinc ions in the zinc salt derivative of the maleic anhydride copolymer are connected with two carboxylic acid groups obtained by ring opening of maleic anhydride in the maleic anhydride copolymer, and the two connected carboxylic acid groups are the same molecular chain and/or two molecular chains.

6. The fluorescent antibacterial polymer material according to claim 1, characterized in that:

the fluorescent antibacterial high polymer material has an excitation wavelength of 330-430 nm, and the strongest emission range of fluorescence is 400-550 nm.

7. The fluorescent antibacterial polymer material according to any one of claims 1 to 6, which is produced by adding a maleic anhydride copolymer to an aqueous solution of an alkali metal hydroxide to react sufficiently, and then adding a zinc salt and/or an aqueous solution of a zinc salt to react sufficiently.

8. The method for preparing fluorescent antibacterial polymer material according to any one of claims 1 to 7, characterized in that the method comprises adding maleic anhydride copolymer into aqueous solution of alkali metal hydroxide for sufficient reaction, and then adding zinc salt and/or aqueous solution of zinc salt for sufficient reaction to generate the zinc salt derivative of maleic anhydride copolymer.

9. The method of claim 8, comprising the steps of:

a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; wherein the weight ratio of the alkali metal hydroxide to the water is (0.1-100): 100, preferably (0.5 to 50): 100, respectively;

b. b, adding the maleic anhydride copolymer into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing for reaction; wherein the weight ratio of the maleic anhydride copolymer to the alkali metal hydroxide is (0.1-20): 1, preferably (0.1 to 10): 1;

c. directly adding zinc salt solid into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;

or taking zinc salt solid, adding the zinc salt solid into water for dissolving to obtain a zinc salt water solution, then adding the zinc salt water solution into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;

wherein the weight ratio range of the zinc salt to the maleic anhydride copolymer is (0.1-20): 1, preferably (0.1 to 10): 1.

10. the method for preparing fluorescent antibacterial polymer material according to claim 9, characterized in that:

in the step a, the alkali metal hydroxide is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, preferably at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide.

11. The method for preparing fluorescent antibacterial polymer material according to claim 9, characterized in that:

in the step b, the maleic anhydride copolymer is selected from maleic anhydride alternating copolymers, preferably at least one alternating copolymer obtained by copolymerizing maleic anhydride and monomers containing isolated carbon-carbon double bonds.

12. The method for preparing fluorescent antibacterial polymer material according to claim 11, characterized in that:

the maleic anhydride alternating copolymer is selected from maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinyl pyrrolidone alternating copolymer and maleic anhydride-itaconic acid alternating copolymer; preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methyl styrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.

13. The method for preparing fluorescent antibacterial polymer material according to claim 9, characterized in that:

in the step c, the zinc salt is at least one water-soluble zinc salt, preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.

14. The fluorescent antibacterial polymer material prepared by the preparation method according to any one of claims 8 to 13.

15. The application of the zinc salt derivative of the maleic anhydride copolymer as the fluorescent antibacterial high polymer material is characterized in that the zinc salt derivative of the maleic anhydride copolymer is the maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups.

16. Use according to claim 15, characterized in that:

the maleic anhydride copolymer is maleic anhydride alternating copolymer and comprises at least one of maleic anhydride linear alternating copolymer and maleic anhydride cross-linked alternating copolymer.

17. Use according to claim 16, characterized in that:

the maleic anhydride alternating copolymer is selected from at least one alternating copolymer obtained by copolymerizing maleic anhydride and a monomer containing isolated carbon-carbon double bonds; preferably maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinylpyrrolidone alternating copolymer, maleic anhydride-itaconic acid alternating copolymer; more preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.

18. Use according to claim 15, characterized in that:

the weight fraction of the zinc element in the maleic anhydride copolymer zinc salt derivative is 10-70%, preferably 20-60%.

19. Use according to claim 15, characterized in that:

divalent zinc ions in the zinc salt derivative of the maleic anhydride copolymer are connected with two carboxylic acid groups obtained by ring opening of maleic anhydride in the maleic anhydride copolymer, and the two connected carboxylic acid groups are the same molecular chain and/or two molecular chains.

20. Use according to claim 15, characterized in that:

the zinc salt derivative of the maleic anhydride copolymer has an excitation wavelength of 330-430 nm, and the strongest emission range of fluorescence of the zinc salt derivative of the maleic anhydride copolymer is 400-550 nm.

21. Use according to claim 15, characterized in that:

the maleic anhydride copolymer zinc salt derivative is prepared by adding a maleic anhydride copolymer into an aqueous solution of alkali metal hydroxide for full reaction, and then adding zinc salt and/or a zinc salt aqueous solution for full reaction.

22. Use according to any one of claims 15 to 21, characterized in that the maleic anhydride copolymer zinc salt derivative is used as a fluorescent antibacterial polymer material in thermoplastic polymer materials, thermosetting polymer materials, rubbers, coatings, inks, security materials.

Technical Field

The invention relates to the technical field of high polymer materials, and in particular relates to a fluorescent antibacterial high polymer material and a preparation method and application thereof.

Background

Along with the increasing environmental protection and health consciousness of people, the killing of microbial pathogens is more and more paid attention. The antibacterial agent is a chemical substance capable of inhibiting or killing microbial pathogens, and scientific researchers can mix the antibacterial agent with plastics, coatings and other carriers to prepare the composite material with the antibacterial effect, so that the antibacterial agent with high efficiency, durability and economy is the key point of research in the antibacterial field.

Antibacterial agents can be classified into three major classes, natural, inorganic and organic. The natural antibacterial agent is mainly extracted from natural plants, and the wide application of the natural antibacterial agent is limited by limited resources. The inorganic antibacterial agent mainly comprises metal silver, zinc and copper metal ion salts, and the metal ions are loaded on the porous material through the actions of physical adsorption, ion exchange and the like, so that the inorganic antibacterial agent has the advantages of high safety, durability, heat resistance and the like, but has poor compatibility with a matrix material and high price.

The organic antibacterial agent comprises quaternary ammonium salts, ureas, guanidines, imidazoles, organic metals and the like, has the characteristics of high sterilization speed, high antibacterial efficiency, convenient processing, stable color and the like, and has the antibacterial mechanism that cations on the organic antibacterial agent are combined with anions on the surface of a cell membrane of bacteria or sulfydryl to destroy the synthesis of proteins and the cell membrane, thereby playing the role of sterilization. However, the organic antibacterial agent often has the defects of easy exudation, poor heat resistance, short service life and the like, and when the organic antibacterial agent is used, porous material loading is often needed, and the long-term antibacterial effect is achieved through slow release. It is clear that if the organic antibacterial agent having a long-lasting effect can be produced without the aid of the carrier loading, it would have an important market value.

Fluorescence is a photoluminescence phenomenon, when a certain substance is irradiated by a certain wavelength, electrons absorb light energy and transit from a ground state to an excited state, and emit emitted light with energy lower than that of incident light in the process of returning to the ground state, so that the fluorescent material can be widely applied to the fields of marking, anti-counterfeiting and the like. The anti-counterfeiting material commonly used at present contains rare earth elements and is high in price, and the fluorescent polymer material is simple to prepare and low in price. Compared with the traditional antibacterial agent, the antibacterial agent with the fluorescence property can be distinguished from other products by ultraviolet lamp irradiation or fluorescence spectrum measurement, has an anti-counterfeiting function, and is convenient for scientific researchers to quickly research the dispersion effect of the antibacterial agent and track the migration path in bacteria.

So far, there are few researches and reports on organic antibacterial agents having fluorescent properties, and therefore, the development of organic antibacterial agents having fluorescent properties with low cost, good heat resistance and long-term durability and the production process thereof will have extremely important market value and economic significance.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a fluorescent antibacterial high polymer material and a preparation method and application thereof. The fluorescent antibacterial high polymer material has both fluorescent characteristic and antibacterial property, and the raw materials and the auxiliary agents in the process are low in price, mature in production process and low in environmental pollution. The preparation method of the fluorescent antibacterial high polymer material is simple and easy to implement, has various application forms, and is extremely easy to industrially popularize.

The invention aims to provide a fluorescent antibacterial high polymer material.

The fluorescent antibacterial high polymer material comprises a maleic anhydride copolymer zinc salt derivative. The zinc salt derivative of the maleic anhydride copolymer is a maleic anhydride copolymer with zinc ions bonded on carboxylic acid groups. The weight percentage of the zinc element in the fluorescent antibacterial polymer material is 10-70%, preferably 20-60%.

The fluorescent antibacterial high polymer material disclosed by the invention has the strongest emission of fluorescence with the excitation wavelength of 330-430 nm of 400-550 nm, and belongs to the blue-green light range.

The maleic anhydride copolymer may be various maleic anhydride copolymers known in the art, and preferably is a maleic anhydride alternating copolymer including at least one of a linear alternating copolymer and a cross-linked alternating copolymer.

The maleic anhydride alternating copolymer is preferably at least one alternating copolymer obtained by copolymerizing maleic anhydride and a monomer containing isolated carbon-carbon double bonds; more preferably maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinylpyrrolidone alternating copolymer, maleic anhydride-itaconic acid alternating copolymer; most preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, and maleic anhydride-isobutylene alternating copolymer.

The molecular structure of the fluorescent antibacterial high polymer material is characterized in that: divalent zinc ions in the maleic anhydride copolymer zinc salt derivative are connected with two carboxylic acid groups obtained by ring opening of maleic anhydride in the maleic anhydride copolymer, and the two connected carboxylic acid groups can be from the same molecular chain or from two molecular chains.

One preferred scheme of the fluorescent antibacterial high polymer material is as follows:

the maleic anhydride copolymer zinc salt derivative of the fluorescent antibacterial high polymer material preferably has the following general formula:

wherein x, y and z are natural numbers, x is more than or equal to 1, and y + z is more than or equal to 0;

the group R₁、R₂、R₄、R₅Is at least one of H and alkyl, preferably at least one of H, methyl and ethyl;

the group R₃、R₆Is H, hydroxy, CH₃COO-, phenyl and/or alkyl, preferably H, hydroxy and CH₃COO-, phenyl, methyl and ethyl;

the zinc ions of the maleic anhydride copolymer zinc salt derivative are combined (connected) with any two of carboxyl groups designated by the first, second, third and fourth, and the carboxyl group combined (connected) with one zinc ion is the same molecular chain or two molecular chains.

The fluorescent antibacterial high polymer material is prepared by adding a maleic anhydride copolymer into an aqueous solution of alkali metal hydroxide for full reaction, and then adding zinc salt and/or a zinc salt aqueous solution for full reaction.

The invention also aims to provide a preparation method of the fluorescent antibacterial high polymer material.

The preparation method of the fluorescent antibacterial high polymer material does not use an organic solvent, and the preparation of the fluorescent antibacterial high polymer material comprises the steps of directly adding a maleic anhydride copolymer solid into an aqueous solution of alkali metal hydroxide for full reaction, and then adding zinc salt and/or a zinc salt aqueous solution for full reaction to obtain the fluorescent antibacterial high polymer material. Specifically, the preparation method of the fluorescent antibacterial polymer material can comprise the following steps:

a. taking alkali metal hydroxide, adding the alkali metal hydroxide into water for dissolving to obtain an alkali metal hydroxide aqueous solution; wherein the weight ratio of the alkali metal hydroxide to the water is (0.1-100): 100, preferably (0.5 to 50): 100, respectively;

b. b, adding the maleic anhydride copolymer into the alkali metal hydroxide aqueous solution prepared in the step a, and fully mixing for reaction; wherein the weight ratio of the maleic anhydride copolymer to the alkali metal hydroxide is (0.1-20): 1, preferably (0.1 to 10): 1; the reaction is acid-base neutralization reaction of carboxylic acid groups of the maleic anhydride copolymer and alkali metal hydroxide;

c. directly adding zinc salt solid into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;

or taking zinc salt solid, adding the zinc salt solid into water for dissolving to obtain a zinc salt water solution, then adding the zinc salt water solution into the mixed solution obtained in the step b, fully mixing and reacting, and separating suspended matters to obtain the fluorescent antibacterial high polymer material;

and c, ion replacement is carried out in the reaction process of the step b, and the alkali metal ions on the reaction product of the alkali metal hydroxide and the maleic anhydride copolymer obtained in the step b are replaced by divalent zinc ions.

Wherein the weight ratio range of the zinc salt (solid) to the maleic anhydride copolymer is (0.1-20): 1, preferably (0.1 to 10): 1.

the concentration of the aqueous solution of zinc salt is not required as long as the amount of zinc salt in water is within the solubility range of zinc salt.

Further, the air conditioner is provided with a fan,

in step a, the alkali metal hydroxide is preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, and more preferably at least one of lithium hydroxide, sodium hydroxide and potassium hydroxide.

In the step b, the maleic anhydride copolymer may be various maleic anhydride copolymers existing in the prior art, preferably maleic anhydride alternating copolymer, more preferably at least one selected from alternating copolymers obtained by copolymerizing maleic anhydride and monomers containing isolated carbon-carbon double bonds, preferably maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer, maleic anhydride-1-butene alternating copolymer, maleic anhydride-2-butene alternating copolymer, maleic anhydride-isobutylene alternating copolymer, maleic anhydride-butadiene alternating copolymer, maleic anhydride-1-pentene alternating copolymer, maleic anhydride-vinyl pyrrolidone alternating copolymer, maleic anhydride-itaconic acid alternating copolymer, more preferably at least one of maleic anhydride-vinyl acetate alternating copolymer, maleic anhydride-styrene alternating copolymer, maleic anhydride-alpha-methylstyrene alternating copolymer and maleic anhydride-isobutylene alternating copolymer.

In general, the maleic anhydride copolymers described can be prepared by methods known in the art, preferably according to the literature: a new family of thermoplastic photoluminescent polymers, Polymer, Chem.,2016,7, 6250-6256; polymer compositions with high haze and high transparency, Polymer. chem.,2015,6,6632-.

In the step c, the zinc salt can be selected from various zinc salts in the prior art, preferably at least one of water-soluble zinc salts, and more preferably at least one of zinc acetate, zinc lactate, zinc chloride, zinc bromide, zinc nitrate, zinc sulfate and zinc gluconate.

In the preparation of the fluorescent antibacterial polymer material, the reaction speed of the maleic anhydride copolymer in the step b and the alkali metal hydroxide is high, and the reaction can be stopped as long as a uniform solution is formed in principle; the time for the sufficient mixing reaction is preferably 0.1 to 12 hours, and more preferably 0.2 to 6 hours. The reaction temperature and the reaction pressure in the step b are not particularly limited, the reaction temperature is preferably 5-95 ℃, the reaction temperature is more preferably room temperature, and the reaction pressure is preferably normal pressure; the apparatus used for the reaction is also not particularly limited, and solution reaction apparatuses in the prior art can be used. The adding speed of the zinc salt in the step c is not particularly limited, and can be fast or slow; the adding process and the stirring speed after adding are not particularly limited, and the stirring speed can be fast or slow or not; the reaction time is not particularly limited since the zinc salt is added and precipitation is generated in the system immediately, but the reaction time affects the yield, and the reaction time is preferably 0.1 to 1 hour, and preferably 0.1 to 0.5 hour. The precipitated product may be separated from the aqueous solution (separation of suspended matter) by methods known in the art, including filtration, centrifugation, and the like; the separated fluorescent antibacterial polymer material can be dried due to containing a little water, the drying temperature and time are not particularly limited as long as the water is removed, and the drying method can be various drying methods in the prior art, including freeze drying, drying and the like.

In the preparation of the fluorescent antibacterial polymer material, various mixing methods and mixing equipment which are commonly used in the prior art can be adopted for the sufficient mixing, and preferably, a common stirring mode and stirring equipment are adopted for the sufficient mixing. Such as mechanical stirring and mixing, centrifugal mixing, magnetic stirring and mixing, and the like, so that the mixture is fully mixed.

In the process of preparing the fluorescent antibacterial high polymer material, when a maleic anhydride copolymer solid is added into an alkali metal hydroxide solution, molecular chains of the maleic anhydride copolymer are not unfolded, more and more carboxylates are generated along with the proceeding of acid-base neutralization reaction of maleic anhydride and the alkali metal hydroxide, and the molecular chains of the copolymer are tangled under the action of hydroxide ions and interact between secondary fluorescent groups (such as C-O, C-O and the like), so that the fluorescent groups are aggregated to form the maleic anhydride copolymer alkali metal salt derivative with fluorescence property; when zinc salt is added to the above aqueous solution of the alkali metal salt derivative of the maleic anhydride copolymer, the alkali metal ions are replaced with zinc ions. The zinc ions are divalent, and can react with two alkali metal carboxylates on the same polymer molecular chain or react with the alkali metal carboxylates on the two polymer molecular chains, and as a result, the cross-linking reaction in the molecular chain and between the molecular chains occurs to the polymer, so that a product (namely, the fluorescent antibacterial high polymer material) is precipitated and separated out from water. The product has a certain amount of zinc element which is an essential element for human body, the safety is high, and the zinc element in the product can be slowly released by the occurrence of cross-linking reaction, so that the long-acting antibacterial effect is kept. Although the alkali metal ions on the alkali metal salt derivative of the maleic anhydride copolymer are replaced by zinc ions, the secondary fluorescent group in the obtained product is still in an aggregation state, and the cross-linking reaction in a molecular chain and among molecular chains can further enhance the aggregation effect, so that the prepared zinc salt derivative of the maleic anhydride copolymer still has the fluorescence property. Furthermore, the obtained fluorescent antibacterial high polymer material has strong absorption in ultraviolet and visible light regions of a spectrum, so that fluorescence group electrons are subjected to excitation transition, excited state electrons interact with zinc element in the process of returning to the ground state, the zinc element is activated, and the binding capacity of zinc and bacterial cell membranes is enhanced, so that the fluorescent antibacterial high polymer material with high safety and lasting antibacterial effect is generated.

The invention also provides the application of the above maleic anhydride copolymer zinc salt derivative as a fluorescent antibacterial high polymer material. The application of the maleic anhydride copolymer zinc salt derivative as a fluorescent antibacterial high polymer material in thermoplastic high polymer materials, thermosetting high polymer materials, rubber, coatings, printing ink and anti-counterfeiting materials is specifically included.

The inventor of the application finds that the fluorescent polymer material with long-acting antibacterial effect can be obtained by performing the two-step modification treatment on the maleic anhydride copolymer. The main advantages of the invention are:

the maleic anhydride copolymer is a byproduct of industrial polyolefin synthesis, and has the advantages of easily obtained raw materials and mature industrial production flow;

secondly, the preparation process of the fluorescent antibacterial high polymer material is simple and easy to implement, and no organic solvent is used; unlike the use of organic solvent, which has high cost, difficult treatment and relatively large environmental pollution; materials involved in the process are all cheap conventional materials, and involved equipment is all common equipment in industrial production;

the fluorescent antibacterial high polymer material has high safety, lasting antibacterial effect and various application ways, can meet application requirements under different conditions, has low production cost and mature process, and is easy to realize industrial production.

The fluorescent antibacterial high polymer material has excellent fluorescence performance, can be simply distinguished from other products through fluorescence phenomenon to have an important anti-counterfeiting effect, and is favorable for quickly detecting the dispersion condition of the fluorescent antibacterial high polymer material in other matrixes.

Drawings

FIG. 1 is a three-dimensional fluorescence spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 1; wherein the ordinate is an excitation interval, and the abscissa is an emission interval;

FIG. 2 is an elemental energy spectrum of the zinc salt derivative of maleic anhydride copolymer prepared in example 1, wherein the ordinate is intensity and the abscissa is energy value of the element, and the corresponding element can be found in a manual according to the energy value;

FIG. 3 is a three-dimensional fluorescence spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 2;

FIG. 4 is a three-dimensional fluorescence spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 3;

FIG. 5 is a three-dimensional fluorescence spectrum of a zinc salt derivative of maleic anhydride copolymer prepared in example 4;

FIG. 6 is a three-dimensional fluorescence spectrum of the fluorescent antibacterial polypropylene composition prepared in example 5;

FIG. 7 is a three-dimensional fluorescence spectrum of a polypropylene blank prepared in comparative example 3;

FIG. 8 is a three-dimensional fluorescence spectrum of a fluorescent antimicrobial polycarbonate composite prepared in example 6;

FIG. 9 is a three-dimensional fluorescence spectrum of the polycarbonate prepared in comparative example 4;

FIG. 10 is a three-dimensional fluorescence spectrum of the fluorescent antimicrobial ink composition prepared in example 7;

FIG. 11 is a three-dimensional fluorescence spectrum of the ink prepared in comparative example 5.

Detailed Description

The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.

1. The experimental data in the examples were determined using the following instruments and methods:

(1) and (3) observation of fluorescence phenomenon: the samples of examples and comparative examples were placed in a dark room and the fluorescence phenomenon was observed under UV irradiation with a UV lamp power of 24W and UV wavelength of 365 nm.

(2) The fluorescence spectrum data adopts JY FL3 fluorescence spectrometer of Japan Horiba company to analyze and test the sample, adopts a 450W xenon lamp light source, the excitation wavelength range is 250-650 nm, and the emission spectrum range is 300-1000 nm.

(3) Powder antibacterial test standard: GB/T21510-; detection bacteria: escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538).

The antibacterial testing step refers to the GB/T21510-2008 standard for testing, and comprises the following specific steps: 1.0g of the sample to be tested was weighed and 5.0mL of the pre-formed bacterial suspension was added. Pouring 1.0mL of the inoculum into an agar culture medium, then culturing for 48 hours in a constant temperature box at 37 ℃, and finally counting viable bacteria on the sample to calculate the antibacterial rate. The blank control group was prepared without the test sample and the other operations were as above.

Testing of antibacterial durability: firstly, a sample to be tested is soaked in distilled water at 50 ℃ for 16 hours, and then the test is carried out according to the GB/T21510-2008 standard.

(4) Antibacterial article test standard: GB/T31402-2015; detection bacteria: escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538P).

An antibacterial testing step, which refers to GB/T31402-2015 standard for testing, and comprises the following specific steps: the samples to be tested were prepared as 50X 50mm samples and the bacterial suspension was diluted with 1/500 nutrient broth for use. 0.4mL of inoculation liquid is dripped on the surface of a sample, a film with the size of 40 multiplied by 40mm is covered, then the sample is covered with a culture dish cover and cultured for 24 hours under the conditions of the temperature of 35 ℃ and the humidity of 90 percent, and finally the viable bacteria on the sample are counted to calculate the antibacterial rate. The blank control group was replaced with a sample without the addition of the fluorescent antibacterial polymer material, and the other operations were the same as above.

Testing of antibacterial durability: firstly, a sample to be tested is soaked in distilled water at 50 ℃ for 16 hours, and then the test is carried out according to the GB/T31402-2015 standard.

(5) Element energy spectrum analysis: element energy spectrum analysis is carried out by using a TEAM electric refrigeration energy spectrometer of EDAX company, corresponding elements can be found in a manual according to energy values, and element content can be measured.

2. Raw materials for examples and comparative examples: