CN106674512B - The method of open loop method building photocatalysis antibacterial stain resistant material - Google Patents

Abstract

The invention discloses a method for constructing a photocatalytic antibacterial and antifouling material by a ring-opening method, and belongs to the technical field of antibacterial and antifouling materials. In the field of antibacterial and antifouling, a photobacterial and antifouling material is constructed based on epoxy and primary ammonia ring-opening polymerization method. Specifically, it relates to a preparation method of a photocatalytic antibacterial agent constructed based on a ring-opening method and its application in the field of surface antibacterial. The method is simple and easy to operate, and the synthesized polymer has high antibacterial and antifouling efficiency.

Description

A method for constructing photocatalytic antibacterial and antifouling materials by ring-opening method

technical field

The invention belongs to the technical field of antibacterial and antifouling materials, in particular to the construction of a series of materials with photocatalytic antibacterial as a matrix and having high-efficiency photocatalytic antibacterial and antifouling effects by a ring-opening method.

Background technique

The use of antibacterial materials can be traced back to a long time ago. The development of antibacterial materials plays an important role in the development of human society and is widely used in people's production and life. Antibacterial agents include natural antibacterial agents, inorganic antibacterial agents, and organic antibacterial agents. Natural antibacterial agents come from some extracts from animals and plants, such as allicin, chitosan, propolis, etc. It is the first antibacterial agent used by humans. Among them, chitosan derived from shrimp shells and crab shells contains active groups in its molecules, which have shown a good inhibitory effect on many bacteria. It is generally believed that its antibacterial mechanism is: the positively charged -NH2 group in the chitosan molecule combines with the dissociated anions such as silicic acid and phosphate contained in the bacterial cell wall, hindering the activity of the bacteria, and then the chitosan passes through The bacterial cell wall enters the bacterial cell and blocks the transition of genetic factors from DNA to RNA, making it impossible to reproduce. Natural antibacterial agents are rich in resources, widely sourced, safe and non-toxic, but due to their short bacteriostatic duration and low efficacy, the large-scale market production of natural antibacterial agents is limited. With the improvement of human research technology and the enhancement of environmental awareness, natural antibacterial agents are bound to receive more and more attention. Inorganic antibacterial agent is a kind of antibacterial agent prepared by using metal ions with bactericidal or bacteriostatic ability such as silver, copper, zinc, titanium, etc. Among them, the widely used inorganic antibacterial agents mainly include: inorganic silver antibacterial agents, TiO2 series photocatalyst antibacterial agents, zinc oxide whisker composite antibacterial agents and other inorganic nano antibacterial agents. Among them, silver-based antibacterial agents are the most widely used. Silver-based antibacterial agents can be divided into two types: compound type and carrier type. According to the different types of carriers, it can be divided into zeolite antibacterial agents, clay antibacterial agents, soluble glass antibacterial agents, and silica gel antibacterial agents. Silver series antibacterial agents have good safety, that is: low toxicity, no irritation, no carcinogenicity, no teratogenicity, etc. In addition, silver series antibacterial agents also have good slow release, broad-spectrum antibacterial properties, good The advantages of heat resistance and processability are favored by researchers. Therefore, the inorganic silver antibacterial agent is currently the most used variety in China. Its mechanism of action is that after the silver ions are slowly released from the carrier, they react with -SH, -NH2 and other sulfur-containing and ammonia-containing functional groups in bacteria and mold cells, hindering protein synthesis and energy sources, and destroying cell membranes or cell protoplasm. enzymatic activity and thus have antibacterial properties. There are many kinds of organic antibacterial agents, mainly including quaternary amine salts, alcohols, phenols, pyridines, isothiazolinone biguanides, organic amines, etc. Organic antibacterial agents are used to irreversibly damage bacteria through chemical reactions, thereby playing the role of sterilization, antiseptic and mildew prevention. Organic antibacterial agents have strong bactericidal power, good effect, and rich sources, but they have shortcomings such as toxicity and poor safety. In addition, they will also cause microorganisms to develop drug resistance, poor heat resistance, and easy migration. The organic surface active antibacterial agents currently studied and used are usually nitrogen-containing cationic compounds, such as quaternary ammonium salts, pyridinium salts, imidazolium salts, isoquinonium salts and other nitrogen-containing heterocyclic salts. The composite antibacterial agent is made by combining different types of antibacterial agents. Through their synergy and complementary advantages, the performance and application scope of the antibacterial agent are improved. The composite antibacterial agent has the advantages of low price, low dosage, good stability, High antibacterial properties.

However, with the development of the times, the drug resistance of bacteria has been increasing in recent years. At the same time, there is a lack of more effective antibacterial drugs. The development of new and effective antibacterial drugs has become imminent. . Although different kinds of antibacterial drugs have been reported in recent years, the strains on which they can effectively act are limited. In addition, in the field of medical devices, the secondary infection of bacteria caused by the adhesion and proliferation of bacteria limits the use conditions of medical devices. An increase in bacterial infection of medically relevant devices that come into contact with the human body is known, and infection is rapidly becoming a major clinical problem. Therefore, antifouling surfaces are useful for clinical applications (such as sutures, surgical products, and wound healing patches) to prevent infection when materials come into contact with wounds or blood. Therefore, it is necessary to develop antibacterial agents with broad-spectrum antibacterial activity against currently common species. materials, and made into antibacterial coatings to achieve antibacterial and sterilization on the surface of medical devices.

With the continuous progress of polymer science, how to better integrate and penetrate it with modern medicine, biology, engineering and other disciplines has become a problem that people focus on solving. In the field of antibacterial, the application of photocatalytic antibacterial materials is not very extensive, mainly nano TiO2, the compatibility of nano TiO2 with various materials, the stable dispersion and storage stability of nano TiO2 in materials, nano TiO2 photocatalytic antibacterial The service life of the material is still insufficient, and the nano-TiO2 photocatalytic material is not widely used in actual industrial production, and further research is needed. Considering the problems of the existing photocatalytic antibacterial agents, it is necessary to develop a new photocatalytic antibacterial agent with superior comprehensive performance.

In recent years, the adhesive proteins secreted by biological mussels can realize the characteristics of surface adhesion of inorganic and organic materials, which has attracted great attention of scientific researchers. Dopamine (DA), a small molecule containing catechol and amino groups, has been demonstrated to act as a precursor of mussel-like adhesion proteins for the development of new mussel biomimetic materials. Under weak alkaline conditions, dopamine and its derivatives are oxidized by dissolved oxygen and spontaneously polymerize to form multifunctional PDA containing catechol units. Due to its excellent adsorption properties, dopamine has been widely used in the modification of antibacterial surfaces and achieved good results. In a mildly alkaline environment under aerobic conditions, dopamine can polymerize on almost any surface to form an adsorbed film polydopamine (PDA). In addition, the exposed reactive groups on the PDA coating were further functionalized by covalently grafting the polymer. The PDA film can undergo Schiff base reaction with the amine group-containing polymer, so that the amine group-containing polymer can be grafted on the film through covalent bonds.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method and application of a photocatalytic antibacterial and antifouling material for ring-opening reaction. The molecular weight of the antibacterial and antifouling agent is controllable, and the effective percentage content of the photocatalytic monomer can be effectively controlled. The antibacterial agent obtained by this method has low antibacterial concentration and obvious bactericidal effect, and can be used for surface modification of glass sheets, polystyrene and the like in combination with the adsorption properties of dopamine to form surface antibacterial polymer brushes. Its antibacterial effect is obvious and has high commercial potential.

The method for constructing a photocatalytic antibacterial and antifouling material by a ring-opening method is characterized in that the polymerization reaction system includes a crosslinking agent, an organic solvent, a polymer monomer A and a polymer monomer B; the whole polymerization reaction is carried out continuously in an oxygen-free environment ; The order of adding the components of the polymerization reaction system is: first dissolve the polymer monomer A and the polymer monomer B in an organic solvent, then add a cross-linking agent, and finally add triethylamine to adjust the reaction environment, so that the polymerization occurs better, After the reaction is completed, add ethylenediamine or ethanolamine to make all the unreacted epoxy react, and polymerize to obtain a polymer containing a BOC group; then dissolve the polymer containing a BOC group in a dichloromethane solution, add trifluoroacetic acid, The BOC group was removed by reaction at room temperature, and the photocatalytic antibacterial and antifouling material was isolated.

The polymer monomer A is an epoxy compound with primary ammonia, the polymer monomer B is N, tert-butoxycarbonyl-1,2 ethylenediamine, and the crosslinking agent is generally polyethylene glycol diglycidyl ether, which can be Select different molecular weights as required.

The mass ratio of the polymer monomer A to the crosslinking agent is in the range of 0.1-20:1, preferably in the range of 0.1-15:1, more preferably in the range of 0.5-10:1; the mass ratio of the polymer monomer B and the crosslinking agent The ratio is in the range of 0.1-25:1, preferably in the range of 0.1-15:1, more preferably in the range of 0.5-10:1; the mass ratio of the organic solvent to the crosslinking agent is in the range of 0.1-200:1, preferably in the range of 1-150:1 , more preferably in the 2-100:1 range.

The polymerization reaction temperature is 0-100°C, preferably 5-95°C, more preferably 10-90°C; the polymerization reaction time is 10-500min, preferably 10-400min, more preferably 30-400min.

In the reaction process, an appropriate amount of triethylamine should be added to provide an alkaline environment for the reaction, and the mass ratio of polymer monomer A to triethylamine is preferably (0.5:8)-(5:15). The quality of adding ethylenediamine or ethanolamine is 1-50 times of the quality of the crosslinking agent,

The polymer monomer A is preferably one or more of primary aminated acid red 87 and primary aminated acid red 94.

The commonly used organic solvent is one or more selected from sulfoxides, amides, and dichloromethane.

The organic solvent is selected from one or more compounds of sulfones, sulfoxides, amides, and alcohols.

The alcohol compound is generally one or more of methanol, ethanol, n-propanol, n-butanol, isopropanol, isobutanol, tert-butanol, isoamyl alcohol, and n-hexanol.

The sulfone compounds are selected from one or more of dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, diphenyl sulfone, dibenzyl sulfone, methyl phenyl sulfone, and sulfolane; the sulfoxides are One or more selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, dipentyl sulfoxide, and dihexyl sulfoxide.

The present invention corresponds to a series of polymers containing BOC groups that are soluble in water, and the general treatment is to dissolve them in water, and the ratio of the amount of water added to the product is 100-300 mL/g, and the products are dissolved and put into dialysis with different molecular weight cutoffs. In order to remove unreacted small molecules, the dialysis process lasted for 3 days, and finally the product in the dialysis bag was freeze-dried until all moisture was removed.

The preparation method of the antibacterial coating of the present invention is as follows: the photocatalytic antibacterial material is formulated into an aqueous solution of an antibacterial agent of 1-4 mg/mL; the substrate is immersed in a Tris-HCl solution of 1-4 mg/mL dopamine, overnight, with The dopamine on the surface is washed off with deionized water, then soaked in a sodium periodate aqueous solution with a concentration of 0.5-1mg/mL for 5-10 minutes, rinsed, and finally soaked in an antibacterial agent aqueous solution for 24h-48h, take out the substrate, remove Rinse with ionized water and blow dry with nitrogen to obtain an antibacterial coating on the surface of the substrate. The material of the substrate is selected from glass, polystyrene, plastic, ceramic, and silicon. The pH value of the Tris-HCl solution is in the range of 7-9, preferably pH=8.5.

In the reaction system of the present invention, the introduction of the amino group in the epoxy ring-opening reaction of primary ammonia starts from the effective photocatalytic antibacterial agent monomer itself, and can be introduced into the effective photocatalytic antibacterial agent monomer by substituting the carboxyl group of the effective photocatalytic antibacterial agent monomer itself. primary amino group, and then proceed to the subsequent ring-opening reaction.

Said type of ring-opening reaction is generally formed by a special functional group on the polymer through a ring-opening reaction. Such polymers usually have a structure containing primary amino groups and epoxy groups, wherein the primary amino groups and epoxy groups can be brought by the polymer itself or attached by chemical reactions.

Beneficial result: the present invention utilizes the ring-opening reaction method to prepare a polymer with a molecular weight of 7000-15000 and a molecular weight distribution of 1.2-1.5. For the ring-opening process: (1) primary amino epoxy ring-opening, or a series of antibacterial polymers obtained by ring-opening reaction of ED, DED or a mixture of any two of them to remove unreacted primary amino groups The skeleton materials are all completely open-loop. (2) The antibacterial agent polymer skeleton material obtained by mixing the ring-opening agent has a controllable ring-opening ratio of the mixed ring-opening agent. (3) In the ring-opening reaction, the percentage of the introduced photocatalytically effective antibacterial agent monomer is controllable and adjustable. (4) All types of antibacterial agents obtained have obvious antibacterial effects, and the MIC value can be as low as 32 μg/L. (6) It can be combined with dopamine to form an antibacterial coating, and the surface antibacterial effect is obvious.

The method is simple and easy to implement, and the polymerization method ensures that the effective photocatalyst is controllable, and the product is resistant to Escherichia coli (E.coil), P. aeruginosa (P. Staphylococcus (S.aureus) and Bacillus subtilis (B.subtilis) have obvious antibacterial effects, and some of the best antibacterial concentrations are as low as 32μg/L. In addition, using the unique adhesion properties of dopamine that can be adhered to almost all materials, after the glass sheet is modified with dopamine, the photocatalytic antibacterial agent with amino groups can interact with the functional groups on the amino group and polydopamine. Antibacterial polymer brushes are formed on surfaces such as vinyl, so as to achieve the effect of anti-fouling on the surface.

Description of drawings

Figure 1 is a graph of the antibacterial rate of EY-PEGDGE-ED with different concentrations in Example 3.

Figure 2 Anti-adherence graph of the antibacterial agent in Example 4 against Escherichia coli under photocatalytic and no photocatalytic conditions.

Detailed ways

The present invention will be further described below in conjunction with the examples, but the present invention is not limited to the following examples.

Example 1

Take 1 mmol of Acid Red 87 and dissolve it in 5 mL of N,N-dimethylformamide (DMF) completely, then dissolve 1.5 mmol of 3-bromopropylamine hydrobromide in the solution, and wrap it with tin foil. The system was reacted at 80°C for 7h, 20mL of ether was added and stirred for 18h, then 20mL of deionized water was added, stirred for 18h, and centrifuged with a centrifuge to remove unreacted acid red 87 and 3-bromopropylamine hydrobromide and most of the Solvent DMF. After centrifugation, the product was dried in a vacuum drying oven for 24 hours and the product was a red powder. This powder is the desired product, denoted as EY-NH2.

Example 2

Take 1mmol of the EY-NH obtained in Example 1 Dissolve in 10mL of DMSO, add 2mmol of polyethylene glycol diglycidyl ether (PEGDGE) and 1mmol of N, tert-butoxycarbonyl-1,2 ethylenediamine to it , and 1 mmol of triethylamine was added, and after 5 minutes of bubbling nitrogen, the system was reacted at 80° C. under magnetic stirring for 3 hours. After that, 2mLED was injected with a syringe to complete the ring-opening reaction of the unreacted primary amino group. At this time, the reaction solution was precipitated with ether and washed twice with ether. The supernatant was removed by centrifugation and the ether was dried to obtain a yellow mucus. Dissolve with a small amount of pure water, then use a 3500 dialysis bag for 2 days to remove ED, then take out the liquid in the dialysis bag and freeze-dried to obtain a red powdery product, which is the product we need, denoted as EY-PEGDGE-ED-BOC .

The polymer (EY-PEGDGE-ED-BOC) had a number average molecular weight (Mn) of 14169 and a molecular weight distribution index (Mw/Mn) of 1.05.

Example 3

Dissolve 1 mmol of EY-PEGDGE-ED-BOC obtained in Example 2 in 10 mL of dichloromethane solution, add 2 mL of trifluoroacetic acid, react at room temperature for 12 h, then remove the dichloromethane solution by rotary evaporation, use ether for precipitation, ultrasonication, centrifugation , thereby removing the -BOC protective group of EY-PEGDGE-ED-BOC to obtain a water-soluble photocatalytic antibacterial and antifouling material, which is denoted as EY-PEGDGE-ED.

Example 4

The water-soluble photocatalytic antibacterial agent EY-PEGDGE-ED obtained in Example 3 was made into 1 mg/mL antibacterial agent aqueous solution for subsequent use; the glass sheet was immersed in the Tris-HCl solution (pH=8.5) of 2 mg/mL dopamine , overnight, washed the surface dopamine with deionized water, then soaked in sodium periodate aqueous solution with a concentration of 1 mg/mL for 10 minutes, rinsed clean, and finally soaked in the above antibacterial agent aqueous solution for 24 hours, took out, and blown with nitrogen Antibacterial coatings modified with different antibacterial agents can be obtained by drying.

The best inhibitory concentration of the antibacterial agent obtained in Example 3 in Escherichia coli (106 bacteria/mL) was 32 μg/mL.

Claims (8)

1. the method for open loop method building photocatalysis antibacterial stain resistant material, which is characterized in that polymerization reaction system includes crosslinking agent, has Solvent, polymer monomer A and polymer monomer B；Entire polymerization reaction is carried out continuously under oxygen-free environment；Polymerization reaction system Each component addition sequence are as follows: polymer monomer A and polymer monomer B are first dissolved in organic solvent, crosslinking agent is then added, finally Triethylamine is added and adjusts reaction environment, makes to polymerize more preferable generation, ethylenediamine or ethanol amine are added after the reaction was completed, makes unreacted Epoxy total overall reaction, polymerization obtains being dissolved in water containing the polymer of BOC group, amount of water and described above poly- The ratio for closing the obtained polymer containing BOC group is 100-300mL/g, and what polymerization described above obtained contains BOC base It is put into bag filter after the polymer dissolution of group to remove the small-molecule substance not reacted, dialysis procedure continues 3 days, finally will The polymers freeze containing BOC group in bag filter is dry until removing all moisture；Then it will contain BOC in bag filter The polymer product of group is dissolved in dichloromethane solution, and trifluoroacetic acid is added, and reaction removing BOC group, isolated at room temperature Photocatalysis antibacterial stain resistant material；

Polymer monomer A is the acid red 87 of primary amine, and polymer monomer B is N- tertbutyloxycarbonyl -1,2 ethylenediamine, crosslinking agent For polyethyleneglycol diglycidylether；Suitable triethylamine should be added in reaction process and provide an alkaline environment for reaction.

2. the method for open loop method building photocatalysis antibacterial stain resistant material described in accordance with the claim 1, which is characterized in that

The mass values of polymer monomer A and crosslinking agent are in 0.1-20:1 range；The mass values of polymer monomer B and crosslinking agent In 0.1-25:1 range；The mass values of organic solvent and crosslinking agent are in 0.1-200:1 range；0-100 DEG C of polymeric reaction temperature； The polymerization reaction time is 10-500min；

The mass ratio of polymer monomer A and triethylamine is (0.5:8)-(5:15)；The quality that ethylenediamine or ethanol amine is added is to hand over Join 1-50 times of agent quality.

3. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 2, which is characterized in that polymerization The mass values of object monomer A and crosslinking agent are 0.1-15:1；The mass ratio of polymer monomer B and crosslinking agent is 0.1-25:1；Have The mass ratio of solvent and crosslinking agent is 1-150:1；5-95 DEG C of polymeric reaction temperature, polymerization reaction time 10-400min.

4. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 2, which is characterized in that polymerization The mass values of object monomer A and crosslinking agent are 0.5-10:1；The mass ratio of polymer monomer B and crosslinking agent is 0.5-10:1；Have The mass ratio of solvent and crosslinking agent is 2-100:1；10-90 DEG C of polymeric reaction temperature, polymerization reaction time 30-400min.

5. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 1, which is characterized in that organic Solvent be selected from sulfone class, sulfoxide type, amides, alcohols one of compound or several.

6. the method for the open loop method building photocatalysis antibacterial stain resistant material according to claim 5, which is characterized in that alcohols Compound be one of methanol, ethyl alcohol, normal propyl alcohol, n-butanol, isopropanol, isobutanol, the tert-butyl alcohol, isoamyl alcohol, n-hexyl alcohol or Person is several；

Sulfone compound is selected from dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, diphenyl sulphone (DPS), dibenzyl sulfone, methyl phenyl sulfone, ring fourth One of sulfone is several；The sulfoxide type be selected from dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, One of diamylsulfoxide, dihexylsulfoxide (DHXSO) are several.

7. the photocatalysis antibacterial stain resistant material being prepared according to any one of claim 1-6 method.

8. preparing the side of antimicrobial coating using the photocatalysis antibacterial stain resistant material that any one of claim 1-6 method is prepared Method, which comprises the following steps: photocatalysis antibacterial material is made into the antibacterial agent aqueous solution of 1-4mg/mL；By substrate It is immersed in the Tris-HCl solution of the dopamine of 1-4mg/mL, overnight, the dopamine on surface is washed with deionized water, then soaks It steeps in the sodium metaperiodate aqueous solution that concentration is 0.5-1mg/mL 5-10 minutes, after rinsing well, is finally immersed in antibacterial agent water - 48h for 24 hours in solution, substrate is taken out, and deionized water is rinsed, and modifies to obtain antimicrobial coating in substrate surface with being dried with nitrogen； The material of the substrate is selected from glass, polystyrene, plastics, ceramics, silicon；The pH value of the Tris-HCl solution is in 7-9 In range.