A surface-modified antibacterial polyurethane material, preparation method and application

Abstract

The present invention discloses a surface-modified antibacterial polyurethane material, a preparation method and an application, belonging to the technical field of the preparation of antibacterial materials. First, an antibacterial modified monomer is prepared, and then a surface hydroxy-rich polyurethane film is prepared. The antibacterial modified monomer is grafted onto the surface of the hydroxy-rich polyurethane film through the coupling reaction between silanol and hydroxyl group, thus obtaining the surface-modified antibacterial polyurethane material. The antibacterial modified monomer is prepared by the ene-thiol click reaction of a silane coupling agent and a quaternary phosphonium salt unsaturated compound. The molar ratio of the silane coupling agent to the quaternary phosphonium salt unsaturated compound is 1 to 3. The polyurethane material of the present invention is safe, environmentally friendly, and has high and lasting antibacterial performance. At the same time, the surface-modified antibacterial polyurethane material has great application prospects in the fields of environmental protection materials, building materials, medical device materials, etc.

Description

Technical Field

[0001] The present invention relates to a surface-modified antibacterial polyurethane material, a preparation method and an application thereof, belonging to the technical field of preparation of antibacterial materials. Background Art

[0002] The large presence of microorganisms and their adhesion to the material surface limit the development of fields such as medical implants, food packaging, and water purification systems, and also threaten people's own health. On the other hand, the frequent use of antibiotics to treat bacterial infectious diseases has led to the large generation of multi-drug resistant strains, and the drug resistance mechanism is complex and changeable, making it difficult to fundamentally solve this problem, which greatly increases the pain and treatment costs of patients. With the continuous progress of science and technology and the increasing improvement of people's living standards, people's self-health awareness is constantly strengthening, and the application of antibacterial materials has gradually attracted people's attention. In daily life, people first come into contact with various materials, such as daily necessities, food packaging, sanitary products, household appliances, public facilities, etc. The handrails encountered when taking the bus and the buttons encountered when taking the elevator have become places for bacteria to breed and spread. In order to prevent the spread of bacteria and reduce cross-infection, it is necessary to advocate the use of antibacterial products in social public places, that is, those functional materials with bacteriostatic and bactericidal properties, so as to improve people's health level and benefit mankind.

[0003] The reproduction of bacteria seriously affects human health. Inorganic metals such as Ag + Although it has antibacterial properties, when it is dispersed in the material, it will migrate, making the antibacterial effect of the material not persistent, and it will cause environmental pollution. Antibacterial agents are divided into inorganic and organic antibacterial agents [CN 107163280 B]. Inorganic antibacterial agents include Ag + 、Cu 2+ 、Zn 2+ , and dispersing them in the material can prepare antibacterial materials. However, after a long time, it will cause the migration of the antibacterial agent, which will not only cause environmental pollution, but also the antibacterial effect cannot be persistent. When it is added to plastic products, the color of the products will change after a long time, affecting their use. Organic antibacterial agents include small molecules such as acids, esters, alcohols, phenols, and quaternary ammonium salts. Adding these small molecules to the material will also cause migration, and they are highly toxic, which greatly limits their use.

[0004] Antibacterial materials are widely used in daily life, especially in thin film materials. Currently, specific functions are generally imparted by coating the material with a coating. Physical effects such as electrostatic adsorption and hydrophobic interaction are used to directly fix functional substances on the material surface. Mohan et al. (Bracic M, Fras-Zemljic L, Perez L, et al. Protein-Repellent and antimicrobial nanoparticle coatings from hyaluronic acid and aLysine-derived biocompatible surfactant[J]. Journal of Materials Chemistry B, 2017, 5:3888-3897.) reported a method for modifying polysiloxane materials. A cationic polymer polyethyleneimine was adsorbed electrostatically, and finally different functional polysaccharides were coated, which had antibacterial effects on Staphylococcus aureus, but there were problems such as non-persistent antibacterial effects. Compared with physical methods, due to the chemical bond between the substrate and the modified material, the chemical modification method can exert its antibacterial function more persistently and stably. In the prior art, mainly high molecular quaternary ammonium salts are chemically bonded to the material, without migration and with persistent antibacterial effects, belonging to contact antibacterial. However, the quaternary ammonium salt monomers carry positive charges and repel each other, and it is not easy to obtain high molecular weight polymers by direct homopolymerization [CN 103232587 A]. At the same time, the research on quaternary ammonium salt antibacterial agents has been quite mature and the applications are also quite extensive. However, their overuse has caused many microorganisms to develop drug resistance to them. Quaternary phosphonium salt antibacterial agents are another type of antibacterial agents after quaternary ammonium salt antibacterial agents. From their structures, the nitrogen atom is replaced by a phosphorus atom, and this difference results in better antibacterial activity of the same type of quaternary phosphonium salts than that of quaternary ammonium salts. Therefore, this patent proposes a preparation method that is simple and can prepare materials with antibacterial properties at the same time. Summary of the Invention

[0005] The object of the present invention is to overcome the above deficiencies and provide a surface-modified antibacterial polyurethane material, a preparation method and an application. The present invention introduces a quaternary phosphonium salt modified monomer with an alkyl chain to covalently modify the surface of the material, effectively improving the antibacterial properties of the material and achieving the purpose of contact antibacterial.

[0006] The technical solution of the present invention:

[0007] A preparation method of a surface-modified antibacterial polyurethane material, wherein the surface-modified antibacterial polyurethane material is obtained by grafting an antibacterial modified monomer onto the surface of a hydroxyl-rich polyurethane film through a coupling reaction between silanol and hydroxyl groups in the antibacterial modified monomer and the hydroxyl-rich polyurethane film, that is, the surface-modified antibacterial polyurethane material is obtained.

[0008] The general structural formula of the antibacterial modified monomer is as follows:

[0009]

[0010] Wherein R1 is one of alkyl (-C m H 2m+1 ), cyclohexyl, or phenyl; R2 is -OCH3 or -OCH2CH3; X is a halogen atom of Br, Cl, or I;

[0011] The surface hydroxy-rich polyurethane film is prepared by the following method: After washing and drying the polyurethane film, it is placed in an oxygen plasma machine for treatment, soaked and dried to obtain the surface hydroxy-rich polyurethane film.

[0012] Furthermore, the composition ratio of the antibacterial modified monomer and the surface hydroxy-rich polyurethane film is:

[0013] The antibacterial modified monomer is 0.1 - 10 parts by weight;

[0014] The surface hydroxy-rich polyurethane film is 100 parts by weight.

[0015] Furthermore, the preparation method of the antibacterial modified monomer: The silane coupling agent and the quaternary phosphonium salt unsaturated monomer are mixed in a molar ratio and added to a solvent, a catalyst is added, and under UV ultraviolet light, through an ene-thiol click reaction, after rotary evaporation, washing, and drying, the antibacterial modified monomer is obtained.

[0016] Furthermore, in the preparation of the antibacterial modified monomer, the molar ratio of the silane coupling agent to the quaternary phosphonium salt unsaturated compound is 1 - 3:1.

[0017] Furthermore, in the preparation of the antibacterial modified monomer: The silane coupling agent is mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane; the quaternary phosphonium salt unsaturated monomer is one or a mixture of two or more of allyltriethylphosphonium bromide, allyltributylphosphonium iodide, allyltricyclohexylphosphonium bromide, or allyltriphenylphosphonium bromide; the catalyst is one of 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, or methyl benzoylformate; the solvent is dichloromethane or chloroform; the washing liquid used is anhydrous ether;

[0018] In the process of the surface hydroxy-rich polyurethane film: The polyurethane film is a highly transparent TPU film; the washing liquid for washing the polyurethane film is one or a mixture of two or more of methanol, ethanol, or water; the soaking liquid is water.

[0019] During the coupling reaction between the silanol and hydroxyl groups of the antibacterial modified monomer and the surface hydroxy-rich polyurethane film: The antibacterial modified monomer and the surface hydroxy-rich polyurethane film are placed in a reaction vessel containing a grafting solution, and reacted at high temperature, washed and dried to obtain a surface-modified antibacterial polyurethane material; the grafting solution is one or more mixtures of anhydrous ethanol, water or toluene; the washing liquid used is one or more of anhydrous ethanol, water or toluene used successively.

[0020] Further, the mass of the catalyst added is 1‰ - 5‰ of the total mass of the silane coupling agent and the quaternary phosphonium salt unsaturated monomer, and the reaction is carried out under a UV ultraviolet lamp with a power of 200W and a wavelength of 365nm for 4 - 10h.

[0021] Further, after the polyurethane film is washed several times in an ultrasonic environment (20 - 80 mL of washing liquid 2), the treatment conditions of the oxygen plasma machine are: treatment at 40 - 80W for 2 - 10min, and the polyurethane film is taken out and immersed in water for 2 - 10min.

[0022] Further, first dissolve the antibacterial modified monomer in the grafting solvent and mix for 0.5h - 4h; then place the surface hydroxy-rich polyurethane film in the grafting solution and react at 40 - 80°C for 6 - 24h.

[0023] The present invention also aims to provide the application of the surface-modified antibacterial polyurethane material prepared by the above method, and the surface-modified antibacterial polyurethane material can be applied to environmental protection materials, building materials, and medical device materials.

[0024] In order to measure the antibacterial performance of the material, the polyurethane material is pre-sterilized under an ultraviolet lamp, and then the antibacterial rate of the film is detected. The quaternary phosphonium salt antibacterial polyurethane obtained according to the preparation method provided by the present invention has the characteristics of high antibacterial rate, long antibacterial timeliness, and non-migration of antibacterial substances.

[0025] The beneficial effects of the present invention:

[0026] 1. The present invention uses a silane coupling agent and a quaternary phosphonium salt unsaturated compound to prepare an antibacterial modified monomer through an ene-thiol click reaction, and accesses it to the polyurethane film by a one-step method, obtaining a quaternary phosphonium cation with hydrophilicity on the surface in a simple process, and at the same time introducing a film material with a long carbon chain, endowing it with antibacterial adhesion performance and improving antibacterial performance.

[0027] 2. The present invention prepares an antibacterial polyurethane material introducing a long alkyl chain of quaternary phosphonium salt in a covalent bonding manner. The radius of the phosphorus atom is larger than that of the nitrogen atom, and the corresponding ionic radius is also larger, with strong polarization, making it easier to lose electrons, increasing the positive charge of the quaternary phosphonium salt, resulting in the quaternary phosphonium salt being more likely to undergo electrostatic adsorption with negatively charged bacteria and kill bacteria, and finally making the material have excellent antibacterial performance.

[0028] 3. The antibacterial polyurethane material prepared by the present invention has simple steps, high antibacterial rate and no migration, is safe to use, and can be applied in various fields such as food packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of QPS4 (antibacterial modified monomer).

[0030] Figure 2 This is the hydrogen NMR spectrum of QPS4 (antibacterial modified monomer).

[0031] Figure 3 The antibacterial test results of TPU-QPS4 (Example 4) and TPU-QPS5 (Comparative Example 1) are shown. DETAILED DESCRIPTION

[0032] The present invention will be further described below in conjunction with the embodiments.

[0033] Example 1

[0034] 0.02 mol of mercaptopropyltrimethoxysilane and 0.01 mol of allyltriethylphosphonium bromide were mixed in 20 mL of dichloromethane, and a catalyst 2,2-dimethoxy-2-phenylacetophenone was added at a mass ratio of 1‰ (the mass ratio of the total amount of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide), and the mixture was reacted under a 200 W UV lamp (365 nm) for 6 hours. The solvent was removed by rotary evaporation, the unreacted products were removed by washing with anhydrous ether, and the antibacterial modified monomer (QPS1) was obtained by drying.

[0035]

[0036] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times under ultrasonic environment (20 mL methanol), placed in an oxygen plasma machine after drying, and treated at 40 W for 4 min. The polyurethane film was taken out and immersed in 5 mL water for 4 min, and dried under inert gas blowing to obtain a surface hydroxyl-rich polyurethane film (TPU1).

[0037] 0.9g QPS1 was dissolved in 5mL grafting solution anhydrous ethanol and mixed for 0.5h; 20g TPU1 was placed in the grafting solution, reacted at 50℃ for 6h, washed 3 times with 20mL anhydrous ethanol, and dried to obtain the surface modified antibacterial polyurethane material TPU-QPS1. Antibacterial tests were carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0038] Example 2

[0039] 0.03 mol of mercaptopropyltriethoxysilane and 0.02 mol of allyltributylphosphonium iodide were mixed in 40 mL of dichloromethane, and methyl benzoylformate with a mass ratio of 3‰ (mass ratio to the total amount of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide) was added as a catalyst. The reaction was carried out under a 200 W UV ultraviolet lamp (365 nm) for 7 h. The solvent was removed by rotary evaporation, and the unreacted substances were removed by washing with anhydrous ether, and then dried to obtain the antibacterial modified monomer (QPS2).

[0040]

[0041] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times in an ultrasonic environment (40 mL of ethanol), dried and then placed in an oxygen plasma machine. It was treated at 50 W for 4 min. The polyurethane film was taken out and immersed in 5 mL of water for 4 min, and then dried under the blowing of inert gas to obtain the surface hydroxy-rich polyurethane film (TPU2).

[0042] 1.2 g of QPS2 was dissolved in 10 mL of grafting solution water and mixed for 0.6 h; 25 g of TPU2 was placed in the grafting solution and reacted at 60 °C for 7 h. It was washed 3 times with 20 mL of anhydrous ethanol and then dried to obtain the surface modified antibacterial polyurethane material TPU-QPS2. And the antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0043] Example 3

[0044] 0.025 mol of mercaptopropyltriethoxysilane and 0.02 mol of allyltricyclohexylphosphonium bromide were mixed in 40 mL of dichloromethane, and 1-hydroxycyclohexyl phenyl ketone with a mass ratio of 3‰ (mass ratio to the total amount of mercaptopropyltrimethoxysilane and allyltricyclohexylphosphonium bromide) was added as a catalyst. The reaction was carried out under a 200 W UV ultraviolet lamp (365 nm) for 8 h. The solvent was removed by rotary evaporation, and the unreacted substances were removed by washing with anhydrous ether, and then dried to obtain the antibacterial modified monomer (QPS3).

[0045]

[0046] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times in an ultrasonic environment (40 mL of water), dried and then placed in an oxygen plasma machine. It was treated at 60 W for 5 min. The polyurethane film was taken out and immersed in 10 mL of water for 4 min, and then dried under the blowing of inert gas to obtain the surface hydroxy-rich polyurethane film (TPU3).

[0047] 1.4g QPS3 was dissolved in 10mL grafting solution anhydrous ethanol and mixed for 0.5h; 23g TPU3 was placed in the grafting solution and reacted at 70℃ for 7h, washed 3 times with 20mL anhydrous ethanol and 20mL water respectively, and dried to obtain the surface modified antibacterial polyurethane material TPU-QPS4. The antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0048] Example 4

[0049] 0.04 mol of mercaptopropyltrimethoxysilane and 0.02 mol of allyltriphenylphosphonium bromide were mixed in 40 mL of dichloromethane, and a catalyst 2,2-dimethoxy-2-phenylacetophenone was added at a mass ratio of 4‰ (the mass ratio of the total amount of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide), and the mixture was reacted under a 200 W UV lamp (365 nm) for 7 hours. The solvent was removed by rotary evaporation, the unreacted products were removed by washing with anhydrous ether, and the antibacterial modified monomer (QPS4) was obtained by drying.

[0050]

[0051] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed three times under ultrasonic conditions (20 mL ethanol and 20 mL water), dried, placed in an oxygen plasma machine, and treated at 50 W for 5 min. The polyurethane film was taken out and immersed in 10 mL water for 5 min, and dried under inert gas blowing to obtain a surface hydroxyl-rich polyurethane film (TPU4).

[0052] 1.4g QPS4 was dissolved in 20mL grafting solution anhydrous ethanol and mixed for 0.5h; 30g TPU4 was placed in the grafting solution and reacted at 65℃ for 7h, washed 3 times with 20mL anhydrous ethanol and 20mL water respectively, and dried to obtain the surface modified antibacterial polyurethane material TPU-QPS4. The antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0053] Comparative Example 1

[0054] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times under ultrasonic environment (20 mL ethanol 20 mL water), placed in an oxygen plasma machine after drying, and treated at 40 W for 6 min. The polyurethane film was taken out and immersed in 10 mL water for 6 min, and dried under inert gas blowing to obtain a surface hydroxyl-rich polyurethane film (TPU5).

[0055] 0.8g of mercaptopropyl trimethoxysilane was dissolved in 20mL of grafting solution anhydrous ethanol and mixed for 0.5h; 30g of TPU5 was placed in the grafting solution and reacted at 65°C for 7h, washed 3 times with 20mL of anhydrous ethanol and 20mL of water respectively, and dried to obtain the surface modified antibacterial polyurethane material TPU-QPS5. Antibacterial tests were carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0056] Comparative Example 2

[0057] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times under ultrasonic environment (20 mL ethanol 10 mL water), placed in an oxygen plasma machine after drying, and treated at 50 W for 4 min. The polyurethane film was taken out and immersed in 10 mL water for 4 min, and dried under inert gas blowing to obtain a surface hydroxyl-rich polyurethane film (TPU6).

[0058] 0.8g of mercaptopropyl triethoxysilane was dissolved in 25mL of grafting solution anhydrous ethanol and mixed for 0.7h; 40g of TPU6 was placed in the grafting solution and reacted at 70°C for 8h, washed 3 times with 20mL of anhydrous ethanol and 10mL of water respectively, and dried to obtain the surface modified antibacterial polyurethane material TPU-QPS6. The antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 1.

[0059] Table 1 Performance of Examples and Comparative Examples

[0060] Antibacterial rate (%) Example 1 44 Example 2 65 Example 3 94 Example 4 100 Comparative Example 1 0 Comparative Example 2 0

[0061] From the performance test data of the above-mentioned embodiments 1-4 and comparative examples 1-2, it can be analyzed that: the antibacterial rate of the polyurethane film that has not been modified with the antibacterial modification monomer is zero; when the number of carbon atoms in the alkyl chain of the quaternary phosphonium salt is 5-6, the polyurethane film has excellent antibacterial performance; when the aromatic ring structure is introduced, the polyurethane film has the best antibacterial performance.

[0062] Example 5

[0063] 0.035 mol of mercaptopropyltrimethoxysilane and 0.025 mol of allyltriphenylphosphonium bromide were mixed in 30 mL of dichloromethane, and a catalyst olefin 2,2-dimethoxy-2-phenylacetophenone was added at a mass ratio of 2‰ (the mass ratio of the total amount of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide), and the mixture was reacted under a 200 W UV lamp (365 nm) for 6 h. The solvent was removed by rotary evaporation, the unreacted product was removed by washing with anhydrous ether, and the mixture was dried to obtain an antibacterial modified monomer (QPS5).

[0064]

[0065] Wash the TPU polyurethane film (Hongda Plastic, 0.2 mm) 3 times in an ultrasonic environment (20 mL of ethanol), dry it, place it in an oxygen plasma machine, treat it at 50 W for 6 min, take out the polyurethane film, immerse it in 10 mL of water for 6 min, and dry it under an inert gas blow to obtain a surface hydroxy-rich polyurethane film (TPU7).

[0066] Dissolve 0.2 g of QPS5 in 20 mL of the grafting solution anhydrous ethanol, and mix for 0.5 h; place 50 g of TPU7 in the grafting solution, react at 60 °C for 6 h, wash 3 times with 20 mL of anhydrous ethanol, and dry to obtain the surface-modified antibacterial polyurethane material TPU-QPS7. And conduct antibacterial tests according to relevant standards, and the antibacterial rate results are listed in Table 2.

[0067] Example 6

[0068] Mix 0.03 mol of mercaptopropyltrimethoxysilane and 0.02 mol of allyltriphenylphosphonium bromide in 30 mL of dichloromethane, add a catalyst 2,2-dimethoxy-2-phenylacetophenone with a mass ratio of 2‰ (the mass ratio of the total amount of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide), react under a 200 W UV ultraviolet lamp (365 nm) for 6 h, remove the solvent by rotary evaporation, wash away the unreacted substances with anhydrous ether, and dry to obtain the antibacterial modified monomer (QPS6).

[0069]

[0070] Wash the TPU polyurethane film (Hongda Plastic, 0.2 mm) 3 times in an ultrasonic environment (20 mL of water), dry it, place it in an oxygen plasma machine, treat it at 40 W for 6 min, take out the polyurethane film, immerse it in 10 mL of water for 6 min, and dry it under an inert gas blow to obtain a surface hydroxy-rich polyurethane film (TPU8).

[0071] Dissolve 0.4 g of QPS6 in 20 mL of the grafting solution anhydrous ethanol, and mix for 0.6 h; place 45 g of TPU8 in the grafting solution, react at 65 °C for 7 h, wash 3 times with 20 mL of anhydrous ethanol, and dry to obtain the surface-modified antibacterial polyurethane material TPU-QPS8. And conduct antibacterial tests according to relevant standards, and the antibacterial rate results are listed in Table 2.

[0072] Example 7

[0073] 0.04 mol of mercaptopropyltriethoxysilane and 0.02 mol of allyltriphenylphosphonium bromide were mixed in 40 mL of dichloromethane. A catalyst, 1-hydroxycyclohexyl phenyl ketone, was added at a mass ratio of 4‰ (based on the total mass of mercaptopropyltrimethoxysilane and allyltriethylphosphonium bromide). The reaction was carried out under a 200 W UV ultraviolet lamp (365 nm) for 8 h. The solvent was removed by rotary evaporation, and the unreacted substances were removed by washing with anhydrous ether. After drying, the antibacterial modified monomer (QPS7) was obtained.

[0074]

[0075] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times in an ultrasonic environment (20 mL of water and 20 mL of ethanol), dried, and then placed in an oxygen plasma machine. It was treated at 60 W for 6 min. The polyurethane film was taken out and immersed in 10 mL of water for 5 min, and then dried under an inert gas flow to obtain a surface hydroxy-rich polyurethane film (TPU9).

[0076] 1.2 g of QPS7 was dissolved in 20 mL of a grafting solution of anhydrous ethanol and water (volume ratio 1:1), and the mixture was stirred for 0.5 h. 45 g of TPU9 was placed in the grafting solution, and the reaction was carried out at 75 °C for 8 h. It was washed 3 times with 20 mL of anhydrous ethanol, and then dried to obtain the surface-modified antibacterial polyurethane material TPU-QPS9. The antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 2.

[0077] Comparative Example 3

[0078] The TPU polyurethane film (Hongda Plastic, 0.2 mm) was washed 3 times in an ultrasonic environment (10 mL of water), dried, and then placed in an oxygen plasma machine. It was treated at 45 W for 6 min. The polyurethane film was taken out and immersed in 10 mL of water for 4 min, and then dried under an inert gas flow to obtain a surface hydroxy-rich polyurethane film (TPU10).

[0079] 1.2 g of mercaptopropyltrimethoxysilane was dissolved in 25 mL of a grafting solution of anhydrous ethanol, and the mixture was stirred for 0.7 h. 40 g of TPU10 was placed in the grafting solution, and the reaction was carried out at 75 °C for 8 h. It was washed 3 times with 20 mL of anhydrous ethanol and 10 mL of water respectively, and then dried to obtain the polyurethane material TPU-QPS10. The antibacterial test was carried out according to relevant standards, and the antibacterial rate results are listed in Table 2.

[0080] Comparative Example 4

[0081] Wash the TPU polyurethane film (Hongda Plastic, 0.2 mm) 3 times in an ultrasonic environment (10 mL of water and 10 mL of absolute ethanol), dry it, and then place it in an oxygen plasma machine. Treat it for 6 min at 55 W. Take out the polyurethane film, immerse it in 15 mL of water for 5 min, and dry it under an inert gas blow to obtain a surface hydroxy-rich polyurethane film (TPU11).

[0082] Dissolve 1.2 g of mercaptopropyltriethoxysilane in 25 mL of grafting solution of absolute ethanol and mix for 0.7 h; place 38 g of TPU11 in the grafting solution and react at 75 °C for 8 h. Wash it 3 times with 20 mL of absolute ethanol and 10 mL of water respectively, and dry it to obtain the polyurethane material TPU-QPS11. And conduct antibacterial tests according to relevant standards, and the antibacterial rate results are listed in Table 2.

[0083] Table 2 Performance of Examples and Comparative Examples

[0084] Antibacterial rate (%) Example 5 48 Example 6 71 Example 7 100 Comparative Example 3 0 Comparative Example 4 0

[0085] From the performance test data of the above Examples 5-7 and Comparative Examples 3-4, it can be analyzed that: the antibacterial rate of the polyurethane film without quaternary phosphonium salt modification is zero; when the number of carbon atoms in the alkyl chain is 5-6, the polyurethane film has excellent antibacterial performance; when an aromatic ring structure is introduced, the polyurethane film has excellent antibacterial performance; with the increase of the content of antibacterial modification monomers, the corresponding increase in the degree of quaternization in the polyurethane chain, the antibacterial property of the polyurethane film is enhanced.

[0086] Those of ordinary skill in the art should understand that: the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of a surface-modified antibacterial polyurethane material, characterized in that, The surface-modified antibacterial polyurethane material is obtained by grafting an antibacterial modified monomer onto the surface of a surface hydroxy-rich polyurethane film through a coupling reaction between silanol and hydroxyl groups in the antibacterial modified monomer and the surface hydroxy-rich polyurethane film, i.e., the surface-modified antibacterial polyurethane material is obtained. The general structural formula of the antibacterial modified monomer is: wherein R1 is one of an alkyl group, a cyclohexyl group, and a phenyl group; R2 is -OCH3 or -OCH2CH3; X is Br, Cl, or I. The surface hydroxy-rich polyurethane film is prepared by the following method: After washing and drying the polyurethane film, it is placed in an oxygen plasma machine for treatment, soaked and dried to obtain the surface hydroxy-rich polyurethane film.

2. The preparation method of a surface-modified antibacterial polyurethane material according to claim 1, characterized in that The composition ratio of the antibacterial modified monomer and the surface hydroxy-rich polyurethane film is: The antibacterial modified monomer is 0.1 - 10 parts by weight; The surface hydroxy-rich polyurethane film is 100 parts by weight.

3. The preparation method of a surface-modified antibacterial polyurethane material according to claim 1, characterized in that, The preparation method of the antibacterial modified monomer: A silane coupling agent and a quaternary phosphonium salt unsaturated monomer are mixed in a molar ratio and added to a solvent, a catalyst is added, and through an ene-thiol click reaction under UV ultraviolet light, the antibacterial modified monomer is obtained after rotary evaporation, washing, and drying.

4. The preparation method of a surface-modified antibacterial polyurethane material according to claim 3, characterized in that, In the preparation of the antibacterial modified monomer, the molar ratio of the silane coupling agent to the quaternary phosphonium salt unsaturated compound is 1 - 3:

1.

5. According to any one of claims 3 - 4, a preparation method of a surface-modified antibacterial polyurethane material, characterized in that In the preparation of the antibacterial modified monomer: The silane coupling agent is mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane; the quaternary phosphonium salt unsaturated monomer is one or a mixture of two or more of allyl triethylphosphonium bromide, allyl tributylphosphonium iodide, allyl tricyclohexylphosphonium bromide, and allyl triphenylphosphonium bromide; the catalyst is one of 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and methyl benzoylformate; the solvent is dichloromethane or chloroform; the washing liquid used is anhydrous ether; In the process of the surface hydroxy-rich polyurethane film: The polyurethane film is a TPU film; the washing liquid for washing the polyurethane film is one or a mixture of two or more of methanol, ethanol, and water; the soaking liquid is water; In the coupling reaction process between the silanol and the hydroxyl group in the antibacterial modified monomer and the surface hydroxy-rich polyurethane film: The antibacterial modified monomer and the surface hydroxy-rich polyurethane film are placed in a reaction vessel containing a grafting solution, and reacted at a high temperature, washed and dried to obtain the surface-modified antibacterial polyurethane material; the grafting solution is one or a mixture of two or more of anhydrous ethanol, water, and toluene; the washing liquids used are one or a mixture of two or more of anhydrous ethanol, water, and toluene used successively.

6. The preparation method of a surface-modified antibacterial polyurethane material according to any one of claims 3-4, characterized in that: The mass of the catalyst added is 1‰ - 5‰ of the total mass of the silane coupling agent and the quaternary phosphonium salt unsaturated monomer, and the reaction is carried out under a UV ultraviolet lamp with a power of 200W and a wavelength of 365nm for 4 - 10h.

7. The preparation method of a surface-modified antibacterial polyurethane material according to any one of claims 3-4, characterized in that: After the polyurethane film is washed in an ultrasonic environment, the treatment conditions of the oxygen plasma machine are: treatment at 40 - 80W for 2 - 10min, and the polyurethane film is taken out and immersed in water for treatment for 2 - 10min.

8. The preparation method of a surface-modified antibacterial polyurethane material according to any one of claims 3-4, characterized in that: First, dissolve the antibacterial modified monomer in the grafting solvent and mix for 0.5 h - 4 h; then place the surface hydroxyl-rich polyurethane film in the grafting solution and react at 40 - 80 °C for 6 - 24 h.

9. The surface-modified antibacterial polyurethane material prepared by any of the methods of claims 1 - 8.

10. Use of the surface-modified antibacterial polyurethane material prepared by any of the methods of claims 1-8, characterized in that: The surface-modified antibacterial polyurethane material can be applied to environmental protection materials, building materials, and medical device materials.

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