CN115124875A - Self-cleaning multi-quaternary phosphonium cation antibacterial coating and preparation method thereof - Google Patents
Self-cleaning multi-quaternary phosphonium cation antibacterial coating and preparation method thereof Download PDFInfo
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Abstract
A self-cleaning multi-quaternary phosphonium cation antibacterial coating and a preparation method thereof belong to the technical field of organic compound antibacterial agents. The antibacterial agent has a structure shown in the following two formulas, wherein a is selected from unsubstituted C2-C8 saturated alkyl chains, and b, C, d and e are selected from unsubstituted C1-C4 saturated alkyl chains; x is halogen, R 1 Selected from hydrogen, methyl, ethyl, methoxyA benzyl group; r 2 Selected from saturated perfluoroalkyl chains of C1-C12. The antibacterial unit of the antibacterial agent has high unit charge density, can more quickly attract bacteria with negative electricity on a cell membrane so as to carry out quick contact sterilization, has good anti-adhesion property, and can effectively prevent the bacteria from being fixedly planted on the surface of a material. The self-cleaning multi-quaternary phosphonium salt designed by the invention can be embedded into the main chain of the material through phenolic hydroxyl or double bonds to realize functional modification of the material, so that the sterilization capability of the material can be improved, and the self-cleaning capability of the material can be enhanced.
Description
Technical Field
The invention belongs to the technical field of organic antibacterial coatings, and particularly designs and prepares a self-cleaning polyquaternary phosphonium cation antibacterial coating.
Background
The results of the study show that the larger atomic radius of P relative to N and the stronger polarization effect compared to the nitrogen atom on the quaternary ammonium salt (QAC) makes the Quaternary Phosphonium Compound (QPC) more readily adsorbed to negatively charged bacterial films, and therefore the high charge density quaternary phosphonium salt exhibits lower resistance to bacteria and a more efficient bactericidal rate than other antibacterial agents (Chemical Engineering Journal,2022,440: 476-492). Meanwhile, fluorine-containing compounds are widely used as effective antibacterial agents for resisting bacterial adhesion, and fluorine-containing long-chain small molecules are super-hydrophobic. The addition of the material can effectively reduce the surface energy of the material, thereby greatly reducing the probability of bacteria attached to the surface of the material (ACS Applied Materials & Interfaces,2021,13(8): 10553-. In addition, the excellent chemical stability of the fluorine-containing compound will also extend the service life of the antibacterial material.
The following are published reports of antibacterial agents and patents relating to self-cleaning and quaternary phosphonium salts:
the document (Biomacromolecules,2022,21:468-482) synthesizes a novel copolymer poly (LAEMA-co-GMA-co-BA) by a simple free radical polymerization method by combining 2-lactonic nano-amide ethyl methacrylamide with a borneol compound with a unique structure. The amine containing silane layer is prepared on the substrate surface by a silanization reaction, followed by grafting of the sugar polymer to the silane layer by covalent bonding, resulting in a glycosylated coating. The prepared coating shows good antibacterial adhesion performance to both E.coli and S.aureus. In addition, no cytotoxicity was observed in vitro against MRC-5 cells (lung fibroblasts), indicating that the antimicrobial coating has good biocompatibility. Its disadvantage is that the antibacterial rate is not very high.
The technology disclosed in the subject group patent (application No. 201910218873.2) shows that the antibacterial monomer is a trihydroxy-containing hexaquaternary phosphonium antibacterial agent, the general structural formula of the quaternary phosphonium cation is shown in formula (2), wherein a and b represent unsubstituted C1-C8 saturated alkyl chains; x is a halogen compound selected from Cl, Br and I. The invention is different from the structure of the invention and has no self-cleaning capability.
None of these documents or patents above relate to the study of self-cleaning multi-quaternary phosphonium salt containing antibacterial coatings. The self-cleaning multi-quaternary phosphonium cation antibacterial coating prepared by the invention can realize synergistic antibacterial by combining tetrahydroxy octaquaternary phosphonium salt cation with high charge density and long fluorine-containing chain and utilizing two different antibacterial mechanisms of contact sterilization and antibacterial adhesion, and is obviously different from the antibacterial coating disclosed in the literature.
Disclosure of Invention
The technical problem to be solved by the invention is that the cationic antibacterial agent can rapidly kill pathogenic microorganisms through contact sterilization, but because the quaternary phosphonium cation is hydrophilic, the probability of bacterial adhesion is increased. Therefore, the bacteria accumulated by electrostatic adsorption form a biofilm covering the material with the lapse of time, resulting in a decrease in antibacterial efficiency. Therefore, an antibacterial material which can sterilize through contact and has a certain degree of anti-adhesion capacity needs to be designed and synthesized. In order to solve the problems, a self-cleaning polyquaternary phosphonium cation antibacterial coating film and a preparation method thereof are provided.
The invention provides a self-cleaning multi-quaternary phosphonium cation antibacterial coating which is characterized by containing an octaquaternary phosphonium cation containing tetrahydroxy and an antibacterial agent containing a long fluorine chain, wherein the antibacterial agent comprises the following components in parts by weight:
in the formula, a represents the carbon number of an unsubstituted saturated alkyl chain of C2-C8, and b, C, d and e represent the carbon number of an unsubstituted saturated alkyl chain of C1-C4; x is halogen, and can be selected from Cl, Br and I; r is 1 Selected from hydrogen, methyl, ethyl, methoxy, benzyl, etc.; r 2 Selected from saturated perfluoroalkyl chains of C1-C12.
The invention provides a preparation method of a self-cleaning polyquaternary phosphonium cation antibacterial coating, which is characterized by comprising the following steps:
a) dissolving the monohydroxy-protected bis-quaternary phosphonium salt having the structure represented by the formula (5) and the compound represented by the formula (6) in an organic solvent, adding an acid-binding agent, and then stirring at 60 ℃ to react. Washing the reacted product by deionized water, collecting an organic layer, drying by a drying agent, washing the reactant by using a large amount of diethyl ether and a large amount of THF, and finally concentrating the solvent;
b) dissolving the product obtained in the step a in an organic solvent, carrying out deprotection on hydroxyl, adjusting the pH value to be neutral, and drying to obtain a target product formula (3);
c) and c, carrying out stirring reaction on the target product in the step b, namely the formula (3) (0.1g-0.5g) with isophorone diisocyanate (0.5g-0.6g), polyether polyol (3.9g-4.27g) and hydroxyethyl acrylate (0.1g) at 60 ℃ to prepare 5g of polyurethane acrylate/tetrahydroxy octaquaternary phosphonium salt oligomer by using dibutyltin dilaurate (30mg) as a catalyst, adding the compound in the formula (4) (0.2g-0.8g) and reactive diluents (TMPTMA1.5g-1.7g, IBOA1.4g-1.6g and HDDA1.0g-1.2g) into the oligomer, and adding a photoinitiator 1173(0.3g) to prepare a final product under the action of ultraviolet light.
Reactive diluents include TMPTMA, IBOA and HDDA.
The mass ratio of the product (3) to isophorone diisocyanate, polyether polyol, hydroxyethyl acrylate is 0.1-0.5: 0.5-0.6: 3.9-4.27: 0.1: 0.030; urethane acrylate/tetrahydroxy octaquaternary phosphonium salt oligomer: a compound of formula (4): TMPTMA: IBOA: HDDA: the mass ratio of the photoinitiator 1173 is 5: 0.2-0.8: 1.5-1.7: 1.4-1.6: 1.0-1.2: 0.3.
the acid-binding agent is selected from potassium carbonate, sodium carbonate, triethylamine and other alkaline reagents, preferably potassium carbonate. The organic solvent in step a can be selected from DMF, dichloromethane and other organic solvents, preferably DMF. The organic solvent in step b can be selected from dichloromethane, trichloromethane and other organic solvents, and dichloromethane is preferred.
The self-cleaning multi-quaternary phosphonium salt ultraviolet light curing antibacterial coating prepared by the invention can be used in a plurality of fields such as medical materials, antibacterial catheters, vehicles, electronic products, home furnishing, ship industry and the like.
Compared with the existing antibacterial agent, the prepared antibacterial agent has the advantages that:
(1) the tetrahydroxy octaquaternary phosphonium salt in the designed self-cleaning multi-quaternary phosphonium salt antibacterial coating has high unit charge density, and can more quickly attract bacteria with negative electricity on a cell membrane, so that the bacteria can be more quickly sterilized.
(2) The long fluorine-containing chain in the designed self-cleaning multi-quaternary phosphonium salt antibacterial coating improves the anti-adhesion property of the material, and can effectively prevent bacteria from being fixedly planted on the surface of the material.
(3) The designed self-cleaning multi-quaternary phosphonium salt antibacterial coating film has good coordinated antibacterial capability and shows excellent antibacterial performance.
Drawings
FIG. 1 shows the hydrogen spectrum and the phosphorus spectrum of the multi-quaternary phosphonium salt of example 1
FIG. 2 is a graph showing total reflection attenuation infrared spectra of self-cleaning polyquaternary phosphonium salt antibacterial coating films prepared in examples 7 to 9 in various ratios. Wherein: a represents a 5 wt% tetrahydroxy octaquaternary phosphonium salt added photocurable coating film, B represents an example 7 photocurable coating film, C represents an example 8 photocurable coating film, and D represents an example 9 photocurable coating film.
FIG. 3 shows the results and inhibition cycles of the self-cleaning polyquaternary phosphonium cation antibacterial agent coating films of examples 1-9 against Staphylococcus aureus and Escherichia coliIntention is. Test bacteria 10 7 CFU/mL s. The test method is a plate counting method, and the antibacterial capacity of the coating film is indicated by the number of colonies on a culture dish. Of these, pure PUA had no antibacterial component and the blank had no bacteria. Panel a represents, from left to right, the antimicrobial results of pure PUA, example 1, example 2 and example 3 photocured films and blank control against both s. Panel B represents, from left to right, the antimicrobial results of pure PUA, example 4, example 5 and example 6 photocurable coating films and blank control against both s. Panel C represents, from left to right, the antimicrobial results of pure PUA, example 7, example 8 and example 9 photocurable coating films and blank control against both s. Graph D represents the size of the inhibition zone of the photo-cured coating films of examples 6, 7, 8 and 9, wherein the larger the inhibition zone, the better the antibacterial property.
FIG. 4 is a graph of anti-adhesion test of films of self-cleaning polyquaternary phosphonium cationic antimicrobial agents to Staphylococcus aureus in examples 7-9 at various ratios. Wherein: panels a-D show the adhesion of staphylococcus aureus to pure PUA, example 7, example 8 and example 9 photocurable coating films, respectively.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Among them, the compound a, the compound B, and the compound C are preferable as the reactants of the examples.
Example 1
Step 1, synthesizing a compound tetrahydroxy octaquaternary phosphonium salt. Taking a 100mL three-neck flask, adding 10mmol of compound A and 2mmol of compound B, and then adding 20mmol of K 2 CO 3 And 50mL of DMF, the reaction was stirred at 60 ℃ for 24 h. After the reaction is finished, using CH 2 Cl 2 The reactants were dissolved. The organic layer is subsequently treated with H 2 Cleaning with water for three times to obtain anhydrous SiO 2 Drying and filteringThe reaction was then washed with copious amounts of diethyl ether and copious amounts of THF, the solvent was concentrated, after which the product was dissolved in CH 2 Cl 2 In the reaction solution, 2 mol. L are added -1 HCl solution, TLC monitor reaction progress, after reaction completion organic layer H 2 And cleaning for three times. Concentrating the solvent to obtain a light yellow tetrahydroxy octaquaternary phosphonium salt solid product;
step 2A 100mL three-necked flask was charged with 0.1g of the tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.53g of isophorone diisocyanate, and the mixture was mechanically stirred and heated to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.27.27 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer obtained in step 2 was uniformly stirred in a beaker with 0.2g of the compound c, 1.7g of a reactive diluent (tmptma, 1.6g of iboa1, 6g of hdda1.2g) and 1173(0.3g) of a photoinitiator in a mass percent of 50/2/45/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a1 wt% tetrahydroxy octaquaternary phosphonium salt/2 wt% fluorine-containing chain/PUA target photocured coating film.
Example 2
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2, a 100mL three-neck flask is taken, 0.1g of tetrahydroxy octaquaternary phosphonium salt prepared in step 1 and 0.53g of isophorone diisocyanate are added, mechanical stirring is carried out, and the temperature is raised to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.27.27 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred in a beaker with 0.5g of the compound c0, 6g of the reactive diluent (tmptma1.6g, iboa1.5g and hdda1.1g) and 1173(0.3g) of the photoinitiator in terms of mass percentage of 50/5/42/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a1 wt% tetrahydroxy octaquaternary phosphonium salt/5 wt% fluorine-containing chain/PUA target photocured coating film.
Example 3
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2A 100mL three-necked flask was charged with 0.1g of the tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.53g of isophorone diisocyanate, and the mixture was mechanically stirred and heated to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.27.27 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred in a beaker with compound C0.8g, reactive diluents (TMPTMA1.5g, IBOA1.4g and HDDA1.0g) and photoinitiator 1173(0.3g) in terms of mass% 50//8/39/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a1 wt% tetrahydroxy octaquaternary phosphonium salt/8 wt% fluorine-containing chain/PUA target photocured coating film.
Example 4
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2, taking a 100mL three-neck flask, adding 0.3g of tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.6g of isophorone diisocyanate, mechanically stirring and heating to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.0.0 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4 hours of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred in a beaker with 0.2g of the compound c, the reactive diluent (tmptma1.7g, iboa1.6g and hdda1.2g) and the photoinitiator 1173(0.3g) in terms of mass percentage of 50/2/45/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 3 wt% tetrahydroxy octaquaternary phosphonium salt/2 wt% fluorine-containing chain/PUA.
Example 5
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2, a 100mL three-neck flask was taken, 0.3g of the tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.6g of isophorone diisocyanate were added thereto, and mechanical stirring was carried out and the temperature was raised to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.0.0 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4 hours of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred in a beaker with 0.5g of the compound c0, 6g of the reactive diluent (tmptma1.6g, iboa1.5g and hdda1.1g) and 1173(0.3g) of the photoinitiator in terms of mass percentage of 50/5/42/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 3 wt% tetrahydroxy octaquaternary phosphonium salt/5 wt% fluorine-containing chain/PUA.
Example 6
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2, a 100mL three-neck flask was taken, 0.3g of the tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.6g of isophorone diisocyanate were added thereto, and mechanical stirring was carried out and the temperature was raised to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 4.0.0 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4 hours of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer 5.0g prepared in step 2 was uniformly stirred in a beaker with compound c0.8g, reactive diluent (tmptma1.5g, ibaa 1.4g and hdda1.0g) and photoinitiator 1173(0.3g) in mass percent of 50/8/39/3 (wt%) for 1 h. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 3 wt% tetrahydroxy octaquaternary phosphonium salt/8 wt% fluorine-containing chain/PUA.
Example 7
Step 1A, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the example 1;
step 2, taking a 100mL three-neck flask, adding 0.5g of tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.5g of isophorone diisocyanate, mechanically stirring and heating to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 3.9.9 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred in a beaker with 0.2g of the compound c, the reactive diluent (tmptma1.7g, iboa1.6g and hdda1.2g) and the photoinitiator 1173(0.3g) in terms of mass percentage of 50/2/45/3 (wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 5 wt% tetrahydroxy octaquaternary phosphonium salt/2 wt% fluorine-containing chain/PUA.
Example 8
Step 1A, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the example 1;
step 2, taking a 100mL three-neck flask, adding 0.5g of tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.5g of isophorone diisocyanate, mechanically stirring and heating to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 3.9.9 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3. 5.0g of the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer prepared in step 2 was uniformly stirred with compound c0.5g, reactive diluent (tmptma1.6g, iboa1.5g and hdda1.1g) and photoinitiator 1173(0.3g) in a beaker according to mass percent (50/5/42/3 wt%) for 1 hour. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 5 wt% tetrahydroxy octaquaternary phosphonium salt/5 wt% fluorine-containing chain/PUA.
Example 9
Step 1, preparing a light yellow tetrahydroxy octaquaternary phosphonium salt solid product by the corresponding method of the embodiment 1;
step 2, taking a 100mL three-neck flask, adding 0.5g of tetrahydroxy octaquaternary phosphonium salt obtained in step 1 and 0.5g of isophorone diisocyanate, mechanically stirring and heating to 60 ℃. After 30 minutes 30mg of dibutyltin dilaurate were added to the flask and the polyether polyol HSH330N 3.9.9 g was slowly added dropwise to the flask via a constant pressure dropping funnel after 4h of reaction. 0.1g of hydroxyethyl acrylate (HEA) was slowly added dropwise to the flask for capping, and after a few minutes it was taken off and cooled to room temperature. 5.0g of tetrahydroxy octaquaternary phosphonium salt/PUA oligomer can be prepared;
step 3 the tetrahydroxy octaquaternary phosphonium salt/PUA oligomer 5.0g prepared in step 2 was uniformly stirred in a beaker with compound c0.8g, reactive diluents (tmptma1.5g, iboa1.4g and hdda1.0g) and photoinitiator 1173(0.3g) in terms of mass% 50/8/39/3 (wt%) for 1 h. After the completion of the stirring, the prepolymer was uniformly coated on a silica gel mold (50 mm. times.50 mm), and in order to prevent oxygen agglomeration during photocuring, the prepolymer was covered with a polyethylene film, followed by exposure to an ultraviolet mercury lamp (optimum time 90 seconds) to obtain a target photocured coating film of 5 wt% tetrahydroxy octaquaternary phosphonium salt/8 wt% fluorine-containing chain/PUA.
The series of coating films of examples 1 to 9 were subjected to an antibacterial test. Test bacteria 10 7 CFU/mL s. As a control group, pure PUA without added antimicrobial agent was used, and as an experimental result, the average value measured by three parallel experiments was used. The result shows that the number of bacterial colonies on the culture dish is obviously reduced along with the increase of the mass fractions of the tetrahydroxy octaquaternary phosphonium salt and the fluorine-containing long chain, and the antibacterial performance of the self-cleaning polyquaternary phosphonium cation photocuring coating film is obviously improved along with the increase of the mass fractions of the tetrahydroxy octaquaternary phosphonium salt and the fluorine-containing long chain. The scanning electron microscope experiment result shows that the adhesion degree of bacteria on the surface of the coating film is obviously reduced along with the increase of the mass fraction of the fluorine-containing chain, and the coating film prepared by the invention has good self-cleaning capability.
Claims (8)
1. An antibacterial agent containing a tetra-hydroxy octaquaternary phosphonium cation and a long fluorine-containing chain, which comprises the following components in formula (3) and formula (4):
in the formula, a represents the carbon number of an unsubstituted saturated alkyl chain of C2-C8, and b, C, d and e represent the carbon number of an unsubstituted saturated alkyl chain of C1-C4; x is halogen, and can be selected from Cl, Br and I; r is 1 Selected from hydrogen, methyl, ethyl, methoxy, benzyl, etc.; r 2 Selected from saturated perfluoroalkyl chains of C1-C12.
2. A self-cleaning polyquaternary phosphonium cationic antimicrobial coating comprising the antimicrobial agent of claim 1.
3. A method for preparing a self-cleaning polyquaternary phosphonium cationic antibacterial coating film containing the antibacterial agent of claim 1, comprising the steps of:
a) dissolving monohydroxy-protected bis-quaternary phosphonium salt with a structure shown in a compound formula (5) and a compound formula (6) in an organic solvent, adding an acid-binding agent, and stirring at 60 ℃ for reaction; washing the reacted product by deionized water, collecting an organic layer, drying by a drying agent, washing the reactant by using a large amount of diethyl ether and a large amount of THF, and finally concentrating the solvent;
b) dissolving the product obtained in the step a in an organic solvent, carrying out deprotection on hydroxyl, adjusting the pH value to be neutral, and drying to obtain a target product formula (3);
c) b, stirring the target product in the step b, namely the formula (3), isophorone diisocyanate, polyether glycol and hydroxyethyl acrylate to react at 60 ℃, taking dibutyltin dilaurate as a catalyst to prepare a polyurethane acrylate/tetrahydroxy octaquaternary phosphonium salt oligomer, adding a compound in the formula (4) and an active diluent into the oligomer, adding a photoinitiator 1173, and then preparing a final product under the action of ultraviolet light;
4. a method according to claim 3, wherein the reactive diluent comprises TMPTMA, IBOA and HDDA.
5. The process according to claim 3, wherein the mass ratio of the product of formula (3) to isophorone diisocyanate, polyether polyol, hydroxyethyl acrylate, catalyst is 0.1-0.5: 0.5-0.6: 3.9-4.27: 0.1: 0.030; urethane acrylate/tetrahydroxy octaquaternary phosphonium salt oligomer: a compound of formula (4): TMPTMA: IBOA: HDDA: the mass ratio of the photoinitiator 1173 is 5: 0.2-0.8: 1.5-1.7: 1.4-1.6: 1.0-1.2: 0.3.
6. a process according to claim 3, characterized in that the acid-binding agent is selected from potassium carbonate, sodium carbonate, triethylamine and other basic agents, preferably potassium carbonate. The organic solvent in step a can be selected from DMF, dichloromethane and other organic solvents, preferably DMF. The organic solvent in step b can be selected from dichloromethane, trichloromethane and other organic solvents, and dichloromethane is preferred.
7. A self-cleaning polyquaternary phosphonium cationic antimicrobial coating film prepared according to the method of any one of claims 3 to 7.
8. Use of the self-cleaning polyquaternary phosphonium cationic antibacterial coating film prepared by the method according to any one of claims 3 to 7 as a self-cleaning antibacterial film.
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