A method for synthesizing POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber

Abstract

The invention discloses a method for synthesizing a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber. Octavinyl POSS, aminothiol, tetrahydrofuran and a photoinitiator are added in sequence, sealed with nitrogen purge, stirred at room temperature for 1 to 12 hours under ultraviolet irradiation, and the solvent is removed. The mixture is immediately diluted with a solvent, cooled to 0°C, and vigorously stirred with 1-3-propane sultone for 24 to 36 hours. The mixture is washed with N,N-dimethylformamide and then with ether. The mixture is vacuum dried, and then a compatibilizing crosslinking agent and polydimethylsiloxane are added and stirred at 60 to 130°C for 1 to 24 hours; a catalyst is then added and stirred for 3 to 5 minutes; the mixture is injected into a mold and cured at room temperature for 1 to 168 hours to obtain a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber. The silicone rubber has good antibacterial and antifouling capabilities and is simple to prepare. The introduction of POSS nanoparticles significantly enhances its mechanical properties, and significantly improves the modulus and tensile strength properties. Compared with traditional small molecule antibacterial materials, it has the advantages of excellent chemical stability and long-term activity.

Description

Technical Field

[0001] The invention relates to the field of antibacterial materials, and in particular to a method for synthesizing POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber. Background Art

[0002] Single-component room temperature curing condensation type silicone sealant is widely used in the interior decoration industry due to its wide range of adhesion and convenient construction. RTV silicone sealant is prone to slippery substances in the part that is immersed in water for a long time. This is an intuitive phenomenon of microorganisms breeding and growing on the surface of the colloid. If the silicone sealant is not treated with mildew and antibacterial treatment, the colloid will accumulate microorganisms for a long time, which may cause the appearance to become black or spotted at the least, or even cause the sealant to fail in performance. For parts that are in contact with water for a long time, it is generally recommended to use mildew-proof silicone sealant. Existing mildew-proof sealants usually add inorganic or organic antibacterial agents, and the most common mode of addition is physical compounding. This type of mildew-proof sealant has a good antibacterial effect in the initial period of time, but the antibacterial effect deteriorates significantly after a long time. This is due to the decline in the quality of the colloid of the physically blended antibacterial agent.

[0003] In addition, quaternary ammonium salts have excellent antibacterial properties and are widely used in antibacterial materials. Antibacterial polymers prepared based on the antibacterial theory of quaternary ammonium salts have strong antibacterial properties. Usually, quaternary ammonium salts are composed of two parts: a hydrophilic part (ammonium cation) and a hydrophobic part (hydrophobic alkyl chains of different lengths). Quaternary ammonium salts destroy the fluidity and permeability of the membrane by combining their hydrophobic long carbon chains into the lipid bilayer structure of the cell membrane. The ammonium cation interacts with negatively charged phospholipids through electrostatic forces and hydrogen bonds, thereby causing inhibition or denaturation of cell membrane proteins.

[0004] The quaternary ammonium salt polymer synthesized by the present invention synthesizes an antibacterial silicone rubber containing quaternary ammonium salt and zwitterion at the same time, wherein the quaternary ammonium salt makes the silicone rubber have better antibacterial effect, and the zwitterion makes the silicone rubber have excellent anti-fouling effect. The product is octavinyl POSS modified by tertiary amine thiol into a compound containing multiple tertiary amine groups, and then mixed with 1-3-propane sultone to generate zwitterion POSS, and then mixed with silicone rubber in a volume-increasing crosslinking agent for crosslinking to form silicone rubber. The present invention has the characteristics of fast, high efficiency and simple process. The structural characteristics of the silicone rubber nanoparticles significantly improve the strength of the silicone rubber. It also has good tissue compatibility, and the obtained polymer has application prospects in the field of biomedical dressings. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synthesizing POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber in view of the deficiencies in the prior art.

[0006] The objective of the present invention is to achieve through the following technical scheme: a method for synthesizing POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber, comprising the following steps:

[0007] (1) Preparation of zwitterionic POSS: 1-3 mmol octavinyl POSS, 6-14 mmol aminothiol and 5-10 ml tetrahydrofuran were added in sequence; after protection from light, 0.16-0.32 mmol photoinitiator was added; after sealing, nitrogen was purged to remove oxygen; the mixture was reacted under ultraviolet irradiation at 365 nm at 25° C. for 1-12 h, and the ultraviolet was turned off; vacuum evaporated at 30-50° C. for 24-48 h to obtain a light yellow liquid; the light yellow liquid was then diluted with 6-10 ml of solvent and cooled to 0° C. to obtain a diluted solution; dissolving 5.2-10 mmol of 1-3-propane sultone in 2 ml of N,N-dimethylformamide to obtain an ester-amine solution; then, under vigorous stirring, dropping the prepared ester-amine solution into the diluted solution in 1-3 times, 1-3 ml each time, and continuously stirring until a white precipitate appears, and then stirring for another 24-36 hours to obtain a precipitate; then washing with N,N-dimethylformamide for 0.5-1 hour, then washing with ether for 0.5-1 hour, and vacuum drying at room temperature for 12-24 hours to obtain a zwitterionic POSS;

[0008] (2) 1.7631-5.2892 g of the zwitterionic POSS prepared in step (1) is dissolved in 3-5 g of a compatibilizing crosslinking agent, and then 10-15 g of polydimethylsiloxane is added, followed by stirring at 60-130° C. for 1-24 h; then 0.05-0.1 g of a catalyst is added, and stirred for 3-5 min to obtain a mixture; the mixture is injected into a mold, and cured at room temperature for 1-168 h to obtain a POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0009] Further, the aminomercaptan is dimethylaminopropylmercaptan, dimethylaminoethylmercaptan, dimethylaminobutylmercaptan, dimethylaminopentylmercaptan, diethylaminoethylmercaptan, diethylaminoethylmercaptan, diethylaminobutylmercaptan, diethylaminopentylmercaptan, diethylaminoethylmercaptan, diethylaminobutylmercaptan, diethylaminopentylmercaptan, diethylaminoethylmercaptan, diethylaminobutylmercaptan or diethylaminopentylmercaptan.

[0010] Furthermore, the compatibilizing crosslinking agent is 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0011] Furthermore, the polydimethylsiloxane is a hydroxyl-terminated polydimethylsiloxane, and its viscosity is 500 cts, 1000 cts, 3000 cts, 5000 cts, 10000 cts or 20000 cts.

[0012] Furthermore, the catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dicedecanoate, tetrabutyl titanate or 2-ethylhexyloxy titanate.

[0013] Furthermore, the solvent is toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide or tetrahydrofuran.

[0014] Furthermore, the photoinitiator is diacetophenone, benzoin dimethyl ether, benzoin diethyl ether, benzoin derivatives, benzil ketal derivatives, α-hydroxyalkyl phenone, α-aminoalkyl phenone, acylphosphine oxide, esterified oxime ketone compound, aromatic peroxyester compound, dialkoxyacetophenone, phenylacetoacetate or diacetophenone.

[0015] The beneficial effects of the present invention are as follows: the silicone rubber contains both quaternary ammonium salt and zwitterion antibacterial silicone rubber, the quaternary ammonium salt makes the silicone rubber have better antibacterial effect, and the zwitterion makes the silicone rubber have excellent anti-fouling effect. The product is octavinyl POSS modified by tertiary amine thiol into a compound containing multiple tertiary amine groups, and then mixed with 1-3-propanesulfone to generate zwitterion POSS, and then mixed with silicone rubber in a volume-increasing crosslinking agent for crosslinking to form silicone rubber. The present invention has the characteristics of fast, high efficiency and simple process. And the structural characteristics of the silicone rubber nanoparticles significantly improve the strength of the silicone rubber. It has good tissue compatibility, and the obtained polymer has application prospects in biomedical dressings. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is the structure diagram of zwitterion POSS;

[0017] Figure 2 This is the antibacterial ability diagram of antibacterial and antifouling silicone rubber against Escherichia coli;

[0018] Figure 3 This is the antibacterial ability diagram of antibacterial and antifouling silicone rubber against Staphylococcus aureus;

[0019] Figure 4 This is the stress-strain diagram of the antibacterial and antifouling silicone rubber;

[0020] Figure 5 This is the H NMR spectrum. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0022] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0023] Example 1

[0024] (1) Preparation of zwitterionic POSS: 1 mmol of octavinyl POSS, 10 mmol of 3-(dimethylamino)-1-propanethiol and 5 mL of dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol of benzoin dimethyl ether was added; after sealing, 99.999% pure nitrogen was purged for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 1 hour, and the ultraviolet light was turned off; vacuum evaporation was carried out at 30°C for 24 hours to obtain a light yellow liquid.

[0025] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide (DMF) and cooled to 0°C to obtain a diluted solution; 5.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution in 3 times, 1 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 24 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 0.5 hours, and then washed with ether for 0.5 hours to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0026] The structure of the zwitterionic POSS prepared in this example is shown in FIG. Figure 1 As shown, it is a compound containing four tertiary amines and four zwitterions.

[0027] (2) 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and the mixture was stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0028] In the present embodiment, 3-(dimethylamino)-1-propanethiol is one of dimethylaminopropanethiol, which is an aminothiol. In the present invention, the aminothiol is dimethylaminopropanethiol, dimethylaminoethylthiol, dimethylaminobutylthiol, dimethylaminopentanethiol, diethylaminoethylthiol, diethylaminoethylthiol, diethylaminobutylthiol, diethylaminopentanethiol, diethylaminoethylthiol, diethylaminoethylthiol, diethylaminobutylthiol or diethylaminopentanethiol.

[0029] In this embodiment, benzoin dimethyl ether is used as a photoinitiator. In the present invention, the photoinitiator is diacetophenone, benzoin dimethyl ether, benzoin diethyl ether, benzoin derivatives, benzyl ketal derivatives, α-hydroxyalkyl phenones, α-aminoalkyl phenones, acylphosphine oxides, esterified oxime ketone compounds, aromatic peroxyester compounds, dialkoxy acetophenones, phenylacetoacetate or diacetophenone.

[0030] In this embodiment, 3-glycidyloxypropyl trimethoxysilane is used as a compatibilizing crosslinking agent. In the present invention, the compatibilizing crosslinking agent is 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyl diethoxy silane or 2-(3,4-epoxycyclohexyl)ethyl triethoxy silane.

[0031] In this embodiment, dioctyltin dilaurate is used as a catalyst. In the present invention, the catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, tetrabutyl titanate or 2-ethylhexyloxy titanate.

[0032] In the present invention, the polydimethylsiloxane is a hydroxyl-terminated polydimethylsiloxane, and its viscosity is 500 cts, 1000 cts, 3000 cts, 5000 cts, 10000 cts or 20000 cts.

[0033] In this embodiment, dry N,N-dimethylformamide is used as the solvent; in the present invention, the solvent is toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide or tetrahydrofuran.

[0034] Example 2

[0035] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-propanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 30°C for 24 hours to obtain a light yellow liquid.

[0036] Then, the light yellow liquid was diluted with 6 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 6.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 36 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 1 hour, and then washed with ether for 1 hour to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0037] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 130° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0038] Example 3

[0039] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 8 mmol 3-(dimethylamino)-1-propanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol dialkoxyacetophenone was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 40°C for 48 hours to obtain a light yellow liquid.

[0040] Then, the light yellow liquid was diluted with 10 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 5.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 24 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 1 hour, and then washed with ether for 1 hour to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0041] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dibutyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0042] Example 4

[0043] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added to a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol α-hydroxyalkyl phenone was added; after sealing, 99.999% pure nitrogen was purged for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0044] Then, the light yellow liquid was diluted with 6 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 7.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 36 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 1 hour, and then washed with ether for 1 hour to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0045] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dibutyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0046] In this embodiment, 3-(dimethylamino)-1-ethanethiol is one of dimethylaminoethanethiol.

[0047] Example 5

[0048] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 8 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol of photoinitiator benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0049] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 5.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 24 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 1 hour, and then washed with ether for 1 hour to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0050] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0051] Example 6

[0052] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 14 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.24 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 4 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0053] Then, the light yellow liquid was diluted with 10 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 7.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution twice, 1.5 ml each time, and stirring was continued. A white precipitate appeared after about 1 hour, and then stirred for another 36 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 1 hour, and then washed with ether for 1 hour to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0054] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0055] Example 7

[0056] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 12 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0057] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 9.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and a white precipitate appeared after about 1 hour, followed by stirring for another 24 hours to obtain a precipitate. Then, the solid was washed with dry N, N-dimethylformamide for 1 hour and then washed with ether for 1 hour to obtain a solid; and then vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0058] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0059] Example 8

[0060] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0061] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 10 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and a white precipitate appeared after about 1 hour, followed by stirring for another 24 hours to obtain a precipitate. Then, the solid was washed with dry N, N-dimethylformamide for 0.5 hours and then washed with ether for 0.5 hours to obtain a solid; and the solid was dried under vacuum at room temperature for 12 hours to obtain zwitterionic POSS.

[0062] 2.0742 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 70° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0063] Example 9

[0064] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0065] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 6 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and a white precipitate appeared after about 1 hour, and then stirred for another 24 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 0.5 hours, and then washed with ether for 0.5 hours to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0066] 3.1113 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 70° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0067] Example 10

[0068] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under 365 nm ultraviolet irradiation for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 30°C for 24 hours to obtain a light yellow liquid.

[0069] Then, the light yellow liquid was diluted with 10 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 7 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and a white precipitate appeared after about 1 hour, followed by stirring for another 24 hours to obtain a precipitate. Then, the solid was washed with dry N, N-dimethylformamide for 0.5 hours and then washed with ether for 0.5 hours to obtain a solid; and then vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0070] 4.1484 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltriethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 120° C. for 24 h. Then 0.06 g of dibutyltin diacetate was added, and the mixture was stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0071] Embodiment 11

[0072] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 10 mmol 3-(dimethylamino)-1-ethanethiol and 5 mL dry tetrahydrofuran were added into a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol benzoin dimethyl ether was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0073] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 6.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution 3 times, 1 ml each time, and 1 ml was added each time. A white precipitate appeared after about 1 hour, and then stirred for another 24 hours to obtain a precipitate. Then, it was washed with dry N, N-dimethylformamide for 0.5 hours, and then washed with ether for 0.5 hours to obtain a solid; and vacuum dried at room temperature for 12 hours to obtain zwitterionic POSS.

[0074] 5.1855 g of the zwitterionic POSS prepared in step (1) was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and 10 g of polydimethylsiloxane was added, followed by stirring at 60° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0075] Example 12

[0076] Preparation of zwitterionic POSS: 1 mmol octavinyl POSS, 12 mmol 3-(dimethylamino)-1-butanethiol and 5 mL dry tetrahydrofuran were added to a 25 mL flask in sequence; the flask was wrapped with aluminum foil, and then 0.16 mmol α-hydroxyalkyl phenone was added; after sealing, purged with 99.999% pure nitrogen for 25 minutes to remove oxygen; then the aluminum foil outside the beaker was removed, and the reaction was carried out at 25°C under ultraviolet irradiation of 365 nm for 2 hours, and the ultraviolet light was turned off; vacuum evaporated at 35°C for 24 hours to obtain a light yellow liquid.

[0077] Then, the light yellow liquid was diluted with 8 ml of dry N, N-dimethylformamide and cooled to 0°C to obtain a diluted solution; 6.2 mmol of 1-3-propane sultone was dissolved in 2 ml of 99.5 wt% N, N-dimethylformamide solution to obtain an ester-amine solution; then, under vigorous stirring, the prepared ester-amine solution was added dropwise to the diluted solution three times, 1 ml each time, and a white precipitate appeared after about 1 hour, followed by stirring for another 24 hours to obtain a precipitate. Then, the solid was washed with dry N, N-dimethylformamide for 0.5 hours and then washed with ether for 0.5 hours to obtain a solid; and the solid was dried under vacuum at room temperature for 12 hours to obtain zwitterionic POSS.

[0078] The zwitterionic POSS prepared in step (1) of 2.0742 was dissolved in 3 g of 3-glycidyloxypropyltrimethoxysilane, and then 10 g of polydimethylsiloxane was added, followed by stirring at 80° C. for 24 h. Then 0.06 g of dioctyltin dilaurate was added, and stirred for 5 min to obtain a mixture. The prepared mixture was injected into a mold and cured at room temperature for 168 h to obtain POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber.

[0079] Figure 2 The antibacterial ability of the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 3 and Example 5 against Escherichia coli (E. coli) was characterized. The test showed that the antibacterial rates were 95.2% and 96.5%.

[0080] Figure 3 The antibacterial ability of the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 3 and Example 5 against Staphylococcus aureus (S. aurues) was characterized, and the test showed that the antibacterial rates were 96.3% and 97.8%. The samples of the present invention have excellent antibacterial properties.

[0081] Figure 4 The POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber adopts a dumbbell-shaped type I specimen, and uses a high and low temperature double-column testing machine to test the sample at room temperature, and the tensile speed is 20mm / min. Z-0 is pure silicone rubber without adding quaternary ammonium salt material; Z-1 is the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 1, Z-2 is the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 5, Z-3 is the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 3, and Z-4 is the POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber prepared in Example 2. Through the test, it can be seen that adding a certain amount of zwitterionic POSS to silicone rubber can greatly improve its elastic modulus and tensile strength. The increase in flexibility is conducive to the use of antibacterial and antifouling silicone rubber in medical dressings and other aspects.

[0082] Figure 5 It is the nuclear magnetic hydrogen spectrum of the compound synthesized from the zwitterion POSS and 1-3-propane sultone in the present invention.

[0083] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for synthesizing POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber, characterized in that: The following steps are involved: (1) Preparation of zwitterionic POSS: 1-3 mmol octavinyl POSS, 6-14 mmol aminothiol and 5-10 ml tetrahydrofuran were added in sequence; after protection from light, 0.16-0.32 mmol photoinitiator was added; after sealing, nitrogen was purged to remove oxygen; the reaction was carried out under ultraviolet irradiation of 365 nm at 25° C. for 1-12 h, and the ultraviolet was turned off; vacuum evaporation was carried out at 30-50° C. for 24-48 h to obtain a light yellow liquid; the light yellow liquid was then diluted with 6-10 ml of solvent and cooled to 0° C. to obtain a diluted solution; 5.2-10 mmol 1-3-propane sultone was dissolved in 2 ml of N,N-dimethylformamide to obtain an ester-amine solution; Then, under vigorous stirring, the prepared ester-amine solution is added dropwise to the diluted solution in 1 to 3 times, 1 to 3 ml is added each time, and stirring is continued until a white precipitate appears, and then stirring is continued for 24 to 36 hours to obtain a precipitate; then, the precipitate is washed with N,N-dimethylformamide for 0.5 to 1 hour, and then washed with ether for 0.5 to 1 hour, and vacuum dried at room temperature for 12 to 24 hours to obtain zwitterionic POSS; (2) dissolving 1.7631-5.2892 g of the zwitterionic POSS prepared in step (1) in 3-5 g of a compatibilizing crosslinking agent, adding 10-15 g of polydimethylsiloxane, and stirring at 60-130° C. for 1-24 h; then adding 0.05-0.1 g of a catalyst, stirring for 3-5 min, to obtain a mixture; injecting the mixture into a mold, and curing at room temperature for 1-168 h to obtain a POSS nanoparticle-reinforced quaternary ammonium salt antibacterial and antifouling silicone rubber; The compatibilizing crosslinking agent is 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane or 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane; The polydimethylsiloxane is a hydroxyl-terminated polydimethylsiloxane, and its viscosity is 500 cts, 1000 cts, 3000 cts, 5000 cts, 10000 cts or 20000 cts.

2. A method for synthesizing a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber according to claim 1, characterized in that: The aminomercaptan is dimethylaminopropylmercaptan, dimethylaminoethylmercaptan, dimethylaminobutylmercaptan, dimethylaminopentylmercaptan, diethylaminoethylmercaptan, diethylaminoethylmercaptan, diethylaminobutylmercaptan, diethylaminopentylmercaptan, diethylaminoethylmercaptan, diethylaminobutylmercaptan or diethylaminopentylmercaptan.

3. A method for synthesizing a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber according to claim 1, characterized in that: The catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, tetrabutyl titanate or 2-ethylhexyloxy titanate.

4. A method for synthesizing a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber according to claim 1, characterized in that: The solvent is toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide or tetrahydrofuran.

5. A method for synthesizing a POSS nanoparticle-enhanced quaternary ammonium salt antibacterial and antifouling silicone rubber according to claim 1, characterized in that: The photoinitiator is diacetophenone, benzoin dimethyl ether, benzoin diethyl ether, benzoin derivatives, benzil ketal derivatives, α-hydroxyalkyl phenone, α-aminoalkyl phenone, acylphosphine oxide, esterified oxime ketone compound, aromatic peroxyester compound, dialkoxy acetophenone, phenylacetoacetate or diacetophenone.

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