CN116217891B - Intrinsic antibacterial epoxy resin precursor, composition, preparation method and application thereof - Google Patents

Abstract

The invention discloses an intrinsic antibacterial epoxy resin precursor, composition, preparation method and application thereof. The intrinsic antibacterial epoxy resin precursor has the structure shown in the following formula: Among them, m and n are independently selected from 1 to 3. The preparation process of the intrinsic antibacterial epoxy resin precursor in the present invention is simple, the operation method is simple, the controllability is good, and it is easy to implement, and is suitable for large-scale industrial production; at the same time, the obtained intrinsic antibacterial epoxy resin precursor is The product obtained by cross-linking and curing with commercial curing agents not only maintains excellent thermodynamic properties, but also has excellent intrinsic antibacterial properties and adhesive properties, and has good application prospects in the field of antibacterial coatings and coatings.

Description

An intrinsic antibacterial epoxy resin precursor, composition and its preparation method and application

Technical field

The invention belongs to the technical field of polymer materials, and relates to an intrinsic antibacterial epoxy resin precursor, composition, preparation method and application thereof, and in particular to an intrinsic antibacterial epoxy resin precursor, composition and cured product. Methods for their preparation, and their use in antibacterial coatings.

Background technique

Epoxy resin is widely used in transportation, construction facilities, aviation, etc. due to its excellent mechanical strength, bonding strength, excellent chemical resistance, heat resistance, and high adhesion to various materials. aerospace and other fields. However, when most commercial epoxy resins are used as coatings, coatings, etc., they often cause large-scale bacterial growth and viral contamination due to the attachment of bacterial contaminants. Even after strict cleaning and disinfection work, it is difficult to eradicate stubborn bacteria. Bacterial biofilm. Therefore, in order to reduce bacterial contamination and attachment and the resulting adverse effects on people, the development of intrinsic antibacterial epoxy resins has become one of the main research focuses of current thermosetting resin functionalization.

Some studies have pointed out that intrinsic antibacterial substances are mainly phenolic substances, and the antibacterial mechanism of phenolic substances mainly achieves antibacterial and antibacterial purposes by destroying cell membranes, exuding contents, condensing the cytoplasm, and changing the osmotic pressure of the cell membrane. Cui and Ngo et al. respectively prepared phenol-type branched chain curing agents using cardanol and phenol branched-chain fatty acid amide as raw materials. The epoxy coating prepared with this method was effective against Escherichia coli, Bacillus subtilis, Gram-positive and Gram-positive bacteria. Negative bacteria have good antibacterial and antibacterial activity [Progress in Organic Coatings, 2018, 115, 9-17; Progress in Organic Coatings, 2020, 141, 105536.]. However, these coatings have problems such as complex preparation routes, large amounts of organic solvents, poor durability, and long curing times, which restrict their practical application. Therefore, providing an intrinsic antibacterial epoxy resin precursor, composition, and cured product with a simple preparation method is an urgent problem to be solved.

Contents of the invention

The main purpose of the present invention is to provide an intrinsic antibacterial epoxy resin precursor, composition, preparation method and application thereof, so as to overcome the shortcomings of the existing technology.

In order to achieve the foregoing invention objectives, the technical solutions adopted by the present invention include:

The embodiment of the present invention provides an intrinsic antibacterial epoxy resin precursor, which has a structure shown in formula (I):

Among them, m and n are independently selected from 1 to 3; R ₁ and R ₂ are independently selected from

R ₃ is selected from *Represents key connection location.

Embodiments of the present invention also provide a method for preparing the aforementioned intrinsic antibacterial epoxy resin precursor, which includes: heating a mixed reaction system containing an epoxy resin precursor, a polyphenol organic acid and an esterification catalyst at 80 to 100°C Carry out dehydration and condensation reaction for 3 to 6 hours to obtain an intrinsic antibacterial epoxy resin precursor.

Embodiments of the present invention also provide an intrinsic antibacterial epoxy resin composition, which includes the aforementioned intrinsic antibacterial epoxy resin precursor and an epoxy curing agent.

Embodiments of the present invention also provide a method for preparing an intrinsic antibacterial epoxy resin cured product, which includes: gradient curing the aforementioned intrinsic antibacterial epoxy resin composition at 25 to 90° C. to prepare an intrinsic antibacterial epoxy resin cured product. Antibacterial epoxy resin cured product.

Embodiments of the present invention also provide an intrinsic antibacterial epoxy resin cured product prepared by the aforementioned preparation method. The intrinsic antibacterial epoxy resin cured product has a glass transition temperature of 25 to 120°C and a tensile strength of It is 10-100MPa, the shear strength is 2-14MPa, the bonding strength is 4-15MPa, the killing rate for Gram-negative bacteria is more than 95%, and the killing rate for Gram-positive bacteria is more than 90% .

Embodiments of the present invention also provide the use of the aforementioned intrinsic antibacterial epoxy resin composition or intrinsic antibacterial epoxy resin cured product in the fields of rail transportation, indoor and outdoor building facilities, or protective coatings for aerospace materials.

Embodiments of the present invention also provide an antibacterial coating, which is obtained by thoroughly mixing the aforementioned intrinsic antibacterial epoxy resin composition and applying it to the surface of a substrate, followed by drying.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The intrinsic antibacterial epoxy resin precursor prepared by the present invention directly uses epoxy resin precursor and phenolic acid substances as raw materials, and is obtained through a simple one-step method. The preparation method is simple, the processing cycle is short, and the controllability is good. , large-scale production can be carried out using ordinary processing equipment;

(2) The phenolic acids used in the present invention are renewable resources and can inhibit many types of pathogenic bacteria. Therefore, the development of this intrinsic antibacterial epoxy resin product has a great impact on the development of the field of antibacterial coatings. It is of great significance and can solve the problems of serious bacterial contamination of existing coatings and difficulty in removing bacterial biofilms;

(3) The present invention does not add any solvent in the process of preparing the epoxy resin precursor and curing the spline, avoiding the use of a large amount of organic solvents, reducing material processing costs and existing health risks.

Description of the drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.

Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the intrinsic antibacterial epoxy resin precursor prepared in Example 1 of the present invention;

Figure 2 is an antibacterial test chart of the intrinsic antibacterial epoxy resin precursor prepared in Examples 1-5 of the present invention.

Detailed ways

In view of the shortcomings of the prior art, the inventor of this case was able to propose the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the present invention. Examples, not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

Specifically, as an aspect of the technical solution of the present invention, an intrinsic antibacterial epoxy resin precursor has a structure shown in formula (I):

Among them, m and n are independently selected from 1 to 3; R ₁ and R ₂ are independently selected from

R ₃ is selected from *Represents key connection location.

When the precursor of the intrinsic antibacterial epoxy resin provided by the invention is used to prepare the epoxy resin, the product obtained has very excellent antibacterial properties, excellent friction resistance and a high glass transition temperature.

Specifically, the epoxy resin obtained based on the intrinsic antibacterial epoxy resin precursor provided by the present invention has greatly improved various properties compared with traditional epoxy resin, especially antibacterial performance, mechanical strength and adhesion. To improve the adhesion properties, the epoxy resin precursor prepared by a simple one-step method using phenolic acids as raw materials and epoxy resin precursor not only has excellent antibacterial properties and adhesion properties, but also has high vitrification Transition temperature has broad application prospects in transportation and living facilities.

Another aspect of the embodiments of the present invention also provides a method for preparing the aforementioned intrinsic antibacterial epoxy resin precursor, which includes: allowing a mixed reaction system containing an epoxy resin precursor, a polyphenol organic acid and an esterification catalyst to Carry out dehydration condensation reaction at 80-100°C for 3-6 hours to obtain an intrinsic antibacterial epoxy resin precursor.

In some preferred embodiments, the epoxy resin precursor has any one of the structures shown in the following formula:

Among them, m and n are independently selected from 1 to 3.

In some preferred embodiments, the epoxy resin precursor includes any of ethylene glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and p-phenylene glycol diglycidyl ether. One or a combination of two or more and not limited to this.

In some preferred embodiments, the polyphenol organic acid includes any one or a combination of two or more of gallic acid, protocatechuic acid, and caffeic acid, and is not limited thereto.

In some preferred embodiments, the esterification catalyst includes any one or a combination of two or more of p-toluenesulfonic acid, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, solid acid, and is not limited thereto.

In some preferred embodiments, the molar ratio of the epoxy resin precursor, polyphenol organic acid and esterification catalyst is 1:0.1~0.5:0.01~0.03.

In summary, the present invention provides an intrinsic antibacterial epoxy resin precursor and its preparation method, which introduces phenolic acid substances into the epoxy resin precursor. Compared with traditional epoxy resins, the polyphenol structure can It gives the epoxy resin excellent antibacterial properties, and the product obtained by cross-linking and curing with the curing agent shows better thermodynamic properties, adhesion properties and anti-bacterial adhesion properties; at the same time, the preparation of the intrinsic antibacterial epoxy resin precursor The method is simple, the operation is easy to understand, the reaction conditions are controllable, it is easy to implement, and it is suitable for large-scale production.

Another aspect of the embodiment of the present invention also provides an intrinsic antibacterial epoxy resin composition, which includes: the aforementioned intrinsic antibacterial epoxy resin precursor and an epoxy curing agent.

In some preferred embodiments, the epoxy curing agent includes an amine curing agent, and the amine curing agent includes polyetheramine D230, polyetheramine D400, diethylene triamine, triethylene tetraamine, and tetraethylene pentamine. , isophorone diamine, manganese diamine, polyamide curing agent, any one or a combination of two or more, and is not limited thereto.

In some preferred embodiments, the ratio of the epoxy equivalent value of the intrinsic antibacterial epoxy resin precursor to the equivalent value of the active hydrogen or anhydride group of the epoxy curing agent is 100: (10~100) .

Furthermore, the intrinsic antibacterial epoxy resin composition mainly includes the following components:

(A) The aforementioned intrinsic antibacterial epoxy resin precursor;

(B) One or more epoxy curing agents;

Wherein, the intrinsic antibacterial epoxy resin precursor has the structure shown in the following formula:

Among them, m and n are selected from 1, 2 or 3; R ₁ and R ₂ are independently selected from

R ₃ is selected from *Represents key connection location.

In some embodiments, the epoxy curing agent of component B is amines, acid anhydrides, etc., but is not limited thereto.

Further, the amine curing agents include polyetheramine D230, polyetheramine D400, diethylene triamine, triethylene tetramine, tetraethylene pentamine, isophorone diamine, menthane diamine and polyamide curing agent. Any one or a combination of two or more agents.

In some embodiments, the epoxy equivalent value (moles) of the intrinsic antibacterial epoxy resin precursor of component A is the same as the active hydrogen or anhydride group equivalent value (moles) of the epoxy curing agent of component B. The proportion range of (number) is 10: (1～10).

Another aspect of the embodiment of the present invention also provides a method for preparing an intrinsic antibacterial epoxy resin cured product, which includes: gradient curing the aforementioned intrinsic antibacterial epoxy resin composition at 25 to 90°C, Preparation of intrinsic antibacterial epoxy resin cured product.

In some preferred embodiments, the gradient curing treatment includes: curing the intrinsic antibacterial epoxy resin composition at 25-50°C for 2 hours, then curing at 50-70°C for 2 hours, and then curing at 70-90°C 2h.

Further, the preparation method of the intrinsic antibacterial epoxy resin cured product is prepared from the following two components:

(A) The aforementioned intrinsic antibacterial epoxy resin precursor;

(B) One or more epoxy curing agents.

In some embodiments, the preparation method of the intrinsic antibacterial epoxy resin cured product includes: mixing the component A intrinsic antibacterial epoxy resin precursor and the component B epoxy curing agent at a temperature range of 25 to 90°C. Mix it thoroughly, brush it on the surface of some materials to form a coating, and dry it at 30 to 100°C.

Some of these materials include, but are not limited to, any of metal, glass, polymer, wood, ceramic tile.

Another aspect of the embodiment of the present invention also provides an intrinsic antibacterial epoxy resin cured product prepared by the aforementioned preparation method. The intrinsic antibacterial epoxy resin cured product has a glass transition temperature of 25 to 120°C. The tensile strength is 10-100MPa, the shear strength is 2-14MPa, and the bonding strength is 4-15MPa. The killing rate against Gram-negative bacteria is over 95%, and the killing rate against Gram-positive bacteria is over 95%. More than 90.

Another aspect of the embodiment of the present invention also provides the aforementioned intrinsic antibacterial epoxy resin composition or intrinsic antibacterial epoxy resin cured product in the field of protective coatings for rail transportation, indoor and outdoor building facilities, or aerospace materials. uses in.

For example, antimicrobial coatings or antimicrobial paints.

Another aspect of the embodiment of the present invention also provides an antibacterial coating, which is obtained by thoroughly mixing the aforementioned intrinsic antibacterial epoxy resin composition and applying it to the surface of a substrate, and then drying it.

Further, the antibacterial coating is composed of the intrinsic antibacterial epoxy resin precursor and the epoxy curing agent in the aforementioned intrinsic antibacterial epoxy resin composition, which are thoroughly mixed in a temperature range of 25 to 90°C, and then used Apply to the surface of the substrate by any method such as roller coating, brush coating, spray coating, dip coating, etc., and then dry at 30 to 100°C.

Further, the material of the substrate includes any one of metal, glass, polymer, wood, and ceramic tiles, but is not limited thereto.

The present invention prepares a series of intrinsic antibacterial epoxy resin precursors and their compositions by processing phenolic acid compounds through a solvent-free "one-pot method", and prepares them by blending the components to form coatings and curing them. Intrinsic antibacterial epoxy coating with excellent antibacterial properties. At the same time, in the present invention, there are a large number of catechol and/or pyrogallol structures in the cross-linked structure of the intrinsic antibacterial epoxy coating, which has a strong affinity similar to polydopamine, the main component of mussel podoprotein. Therefore, it not only exerts antibacterial and antibacterial effects, but also shows excellent bonding effects with a variety of materials including metal, glass, polymer, wood, ceramic tiles, etc.

The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and the accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention and provides detailed implementation modes and specific operating processes. However, the present invention The scope of protection is not limited to the following examples.

The experimental materials used in the following examples can be purchased from conventional biochemical reagent companies unless otherwise specified.

Example 1

Place 1 part of ethylene glycol diglycidyl ether, 1 part of 3,4-dihydroxybenzoic acid and 0.01 part of p-toluenesulfonic acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 90°C After 10 hours, intrinsic antibacterial epoxy resin precursor 1 was obtained with a yield of 80%. Its structural formula is as follows:

The obtained product was evacuated in the oven for two hours, and the NMR spectrum of the obtained product is shown in Figure 1. From Figure 1, it can be seen that the monomer was successfully prepared.

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent polyetheramine D230 at a molar ratio of one to one between epoxy and amine active hydrogen, then heat and solidify in a blast oven at room temperature to 80°C. Keep the temperature at 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 25°C, the tensile strength is 10MPa, the shear strength is 12MPa, and the bonding strength is 13MPa. The obtained cured product is subjected to an antibacterial test with a blank sample, and the result The epoxy cured product has an inhibition rate of 95.6% against E. coli and a sterilization rate of 93.5% against Staphylococcus aureus. The antibacterial performance diagram is shown in Figure 2.

Example 2

Place 2 parts of bisphenol A diglycidyl ether, 1 part of 3,4,5-trihydroxybenzoic acid and 0.05 part of phosphoric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 100°C for 8 hours. The intrinsic antibacterial epoxy resin precursor 2 was obtained with a yield of 85% and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and polyetheramine D400 at a molar ratio of one to one between epoxy and amine active hydrogen, then heat and solidify in a blast oven at intervals of 20°C from room temperature to 100°C. Keep the temperature for 2 hours for gradient temperature curing to obtain an epoxy resin cured product. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 120°C, the tensile strength is 100MPa, the shear strength is 14MPa, and the bonding strength is 15MPa. The obtained cured product is subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli was 95.3%, and the sterilization rate against Staphylococcus aureus was 94.7%. The antibacterial performance diagram is shown in Figure 2.

Example 3

Place 3 parts of ethylene glycol diglycidyl ether, 1 part of 3,4,5-trihydroxybenzoic acid and 0.01 part of sulfuric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 100°C for 5 hours. The intrinsic antibacterial epoxy resin precursor 3 was obtained with a yield of 89% and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent diethylenetriamine at a molar ratio of one to one between epoxy and amine active hydrogen, and then heat and solidify in an air blast oven at intervals from room temperature to 60°C. Keep the temperature at 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 34°C, the tensile strength is 25MPa, the shear strength is 14MPa, and the bonding strength is 15MPa. The obtained cured product is subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli is 93.6%, and the sterilization rate against Staphylococcus aureus is 92.3%. The antibacterial performance diagram is shown in Figure 2.

Example 4

Place 5 parts of bisphenol F diglycidyl ether, 1 part of 3,4-dihydroxybenzoic acid and 0.1 part of nitric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 90°C for 8 hours to obtain this product Typical antibacterial epoxy resin precursor 4, with a yield of 93%, and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent triethylenetetramine at a molar ratio of one to one between epoxy and amine active hydrogen, and then heat and solidify in a blast oven at room temperature to 60°C. Keep the temperature at 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 110°C, the tensile strength is 86MPa, the shear strength is 12MPa, and the bonding strength is 13MPa. The obtained cured product was subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli is 92.5%, and the sterilization rate against Staphylococcus aureus is 90.1%. The antibacterial performance diagram is shown in Figure 2.

Example 5

Place 10 parts of bisphenol F diglycidyl ether, 1 part of 3,4-dihydroxyphenyl acrylic acid and 0.2 parts of hydrochloric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 100°C for 6 hours to obtain Intrinsic antibacterial epoxy resin precursor 5 has a yield of 89.5% and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent tetraethylene pentamine at a molar ratio of one to one between epoxy and amine active hydrogen, and then heat and solidify in a blast oven at room temperature to 40°C. Keep the temperature at 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 105°C, the tensile strength is 82MPa, the shear strength is 14MPa, and the bonding strength is 14MPa. The obtained cured product was subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli is 94.9%, and the sterilization rate against Staphylococcus aureus is 94.6%. The antibacterial performance diagram is shown in Figure 2.

Example 6

Place 13 parts of terephthalenedimethanol diglycidyl ether, 1 part of 3,4-dihydroxyphenylacrylic acid and 0.01 part of sulfuric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 100°C for 6 hours. The intrinsic antibacterial epoxy resin precursor 5 was obtained with a yield of 88.7% and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent isophorone diamine at a molar ratio of one to one between epoxy and amine active hydrogen, then heat and solidify in a blast oven at room temperature to 100 The temperature was maintained at an interval of 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 76°C, the tensile strength is 54MPa, the shear strength is 8MPa, and the bonding strength is 11MPa. The obtained cured product was subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli was 91.2%, and the sterilization rate against Staphylococcus aureus was 89.7%.

Example 7

Place 5 parts of bisphenol F diglycidyl ether, 1 part of 3,4,5-trihydroxybenzoic acid and 0.1 part of nitric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 90°C for 8 hours. The intrinsic antibacterial epoxy resin precursor 4 was obtained with a yield of 93% and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and the curing agent Mengdiamine at a molar ratio of one to one between epoxy and amine active hydrogen, and then heat and solidify in a blast oven at room temperature to 80°C. Keep the temperature at 20°C for 2 hours for gradient temperature curing to obtain a cured epoxy resin. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 112°C, the tensile strength is 88MPa, the shear strength is 11MPa, and the bonding strength is 12MPa. The obtained cured product was subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli was 98.1%, and the sterilization rate against Staphylococcus aureus was 95.6%.

Example 8

Place 3 parts of ethylene glycol diglycidyl ether, 1 part of 3,4,5-trihydroxybenzoic acid and 0.01 part of sulfuric acid in a three-necked flask with mechanical stirring and nitrogen purging, and react at 100°C for 5 hours, the intrinsic antibacterial epoxy resin precursor 3 was obtained with a yield of 89%, and its structural formula is as follows:

Mix the obtained intrinsic antibacterial epoxy resin precursor and polyamide curing agent evenly according to the molar ratio of epoxy and amine active hydrogen to one to one, and then heat and solidify in a blast oven at intervals of 20°C from room temperature to 60°C. Keep the temperature for 2 hours for gradient temperature curing to obtain an epoxy resin cured product. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 33°C, the tensile strength is 46MPa, the shear strength is 11MPa, and the bonding strength is 12MPa. The obtained cured product was subjected to an antibacterial test with a blank sample, and the result The sterilization rate of the epoxy cured product against Escherichia coli was 95.1%, and the sterilization rate against Staphylococcus aureus was 93.6%.

Comparative example 1

Mix the ethylene glycol diglycidyl ether and the curing agent polyetheramine D230 at a molar ratio of one to one between epoxy and amine active hydrogen, and then heat and solidify in a blast oven. Keep the temperature at 20°C for 2 hours between room temperature and 80°C. Carry out gradient temperature curing to obtain an epoxy resin cured product. The glass transition temperature of the intrinsic antibacterial epoxy resin cured product is 21°C, the tensile strength is 20MPa, the shear strength is 4MPa, and the bonding strength is 6MPa. The inhibition rate of the obtained cured product against E. coli is 0 %, the bactericidal rate against Staphylococcus aureus is 0%.

In addition, the inventor of the present case also conducted experiments with other raw materials, process operations, and process conditions mentioned in this specification with reference to the aforementioned embodiments, and achieved relatively ideal results.

It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation examples. Any technical modifications made based on the technical solution of the present invention without departing from the purport of the present invention and the scope protected by the claims will fall within the scope of this invention. within the scope of protection of the invention.

Claims (15)

1. An intrinsic antibacterial epoxy resin precursor, characterized in that the intrinsic antibacterial epoxy resin precursor has a structure as shown in formula (I): Among them, m and n are independently selected from 1 to 3; R ₁ and R ₂ are independently selected from R ₃ is selected from *Represents key connection location. 2. The preparation method of intrinsic antibacterial epoxy resin precursor according to claim 1, characterized by comprising: The mixed reaction system including the epoxy resin precursor, polyphenol organic acid and esterification catalyst is subjected to a dehydration condensation reaction at 80 to 100°C for 3 to 6 hours to prepare an intrinsic antibacterial epoxy resin precursor. 3. The preparation method according to claim 2, characterized in that: the epoxy resin precursor has any one of the structures shown in the following formula: Among them, m and n are independently selected from 1 to 3. 4. The preparation method according to claim 2, characterized in that: the epoxy resin precursor is selected from the group consisting of ethylene glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, p- Any one or a combination of two or more benzene glycol diglycidyl ethers. 5. The preparation method according to claim 2, characterized in that the polyphenol organic acid is selected from any one or a combination of two or more of gallic acid, protocatechuic acid and caffeic acid. 6. The preparation method according to claim 2, characterized in that: the esterification catalyst is selected from any one or two or more of p-toluenesulfonic acid, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid and solid acids. combination. 7. The preparation method according to claim 2, characterized in that: the molar ratio of the epoxy resin precursor, polyphenol organic acid and esterification catalyst is 1:0.1~0.5:0.01~0.03. 8. An intrinsic antibacterial epoxy resin composition, characterized by comprising: the intrinsic antibacterial epoxy resin precursor according to claim 1 and an epoxy curing agent. 9. The intrinsic antibacterial epoxy resin composition according to claim 8, characterized in that: the epoxy curing agent is selected from amine curing agents, and the amine curing agent is selected from polyetheramine D230, poly Any one or a combination of two or more of etheramine D400, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, isophorone diamine, menthane diamine, and polyamide curing agent. 10. The intrinsic antibacterial epoxy resin composition according to claim 8, characterized in that: the epoxy equivalent value of the intrinsic antibacterial epoxy resin precursor and the active hydrogen or acid anhydride of the epoxy curing agent The ratio of the equivalent values of the groups is 100: (10～100). 11. A method for preparing an intrinsic antibacterial epoxy resin cured product, which is characterized by comprising: conducting the intrinsic antibacterial epoxy resin composition according to any one of claims 8 to 10 at 25 to 90°C. Gradient curing is used to prepare intrinsic antibacterial epoxy resin cured product. 12. The preparation method according to claim 11, wherein the gradient curing treatment includes: curing the intrinsic antibacterial epoxy resin composition at 25-50°C for 2 hours, and then curing at 50-70°C. 2h, then solidify at 70~90℃ for 2h. 13. The intrinsic antibacterial epoxy resin cured product prepared by the preparation method of claim 11 or 12, characterized in that: the intrinsic antibacterial epoxy resin cured product has a glass transition temperature of 25 to 120 ℃, the tensile strength is 10~100MPa, the shear strength is 2~14MPa, the bonding strength is 4~15MPa, the killing rate of Gram-negative bacteria is more than 95%, and the killing rate of Gram-positive bacteria is The rate is above 90%. 14. The intrinsic antibacterial epoxy resin composition according to any one of claims 8 to 10 or the intrinsic antibacterial epoxy resin cured product according to claim 13 for use in rail transportation, indoor and outdoor construction facilities or aviation Used in the field of protective coatings for aerospace materials. 15. An antibacterial coating, characterized in that: the antibacterial coating is fully mixed with the intrinsic antibacterial epoxy resin composition according to any one of claims 8-10 and applied to the surface of the substrate, and then dried Processing obtained.