Super-lubricating gel with antibacterial function and preparation method thereof

Abstract

The invention relates to super-lubricating gel with an antibacterial function and a preparation method of the super-lubricating gel. The super-lubricating gel is prepared from the following raw material components: QA-GelMA, a vinyl pyrrolidone monomer, N, N '-methylene bisacrylamide and ammonium persulfate, water-soluble super-lubricating molecular polyvinyl pyrrolidone is covalently grafted to gelatin macromolecular chains with carbon-carbon double bonds, and meanwhile, the polyvinyl pyrrolidone macromolecular chains are connected into a network structure through N, N '-methylene bisacrylamide molecules, so that the water-soluble super-lubricating molecular polyvinyl pyrrolidone is prevented from being dissolved and lost in a water body; the purposes of long-term lubrication and resistance reduction are achieved; besides, an epoxy group in 2, 3-epoxypropyl-trimethyl ammonium chloride molecules reacts with gelatin molecules to generate gelatin quaternary ammonium salt, and the quaternary ammonium salt has a good growth inhibition effect on microorganisms such as escherichia coli and staphylococcus aureus, so that long-term super lubrication and resistance reduction are synergistically realized.

Description

Technical Field

[0001] The present invention relates to the technical field of surface engineering lubricating coatings, and particularly relates to a superlubricating gel with antibacterial function and a preparation method thereof. Background Art

[0002] When a ship is sailing, it generally encounters three types of resistance: wave-making resistance, pressure drag, and frictional resistance. Wave-making resistance is mainly a problem encountered in high-speed surface navigation. Improving the design of the vehicle can reduce wave-making resistance; designing the vehicle into a streamlined shape can reduce pressure drag, that is, the pressure difference between the head and the tail of the vehicle when it moves; frictional resistance comes from the interaction between the vehicle and the surrounding water flow. For general ships, frictional resistance accounts for about 70% - 80% of the total resistance. Therefore, reducing surface friction is crucial for overall underwater drag reduction. The realization of drag reduction through lubricating coating technology has attracted great interest among scientific researchers. At the same time, inhibiting the adhesion and growth of bacteria and other microorganisms is of great value for reducing the navigation resistance of ships.

[0003] Therefore, the research and development of a superlubricating gel with antibacterial function not only inhibits the adhesion and growth of bacteria and other microorganisms, but also can play a role in lubricating drag reduction, enabling the two to produce a synergistic enhancement effect, which is beneficial to achieving long-term lubricating drag reduction and has important practical application value.

[0004] Existing lubricating coatings, such as a water-based medical hydrophilic lubricating coating and its preparation method disclosed in the patent application with the publication number CN102973987B, in which the coating selects water-soluble macromolecules such as polyacrylamide, polyvinylpyrrolidone or polyethylene glycol, and at the same time adds water-based surfactants: trisodium phosphate, sodium hexametaphosphate, alkylphenol polyethylene ether, alkyl polyoxyethylene ether, polyoxyethylene alkyl ester, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium lauryl sulfate, and water-based thickeners: methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose, polyacrylic acid. However, the water-soluble macromolecules used in this formulation are prone to loss, resulting in unstable lubricating effects, and there is no antibacterial function. After microbial colonization, the lubricating performance will decline. Summary of the Invention

[0005] In order to overcome the defects of the above-mentioned prior art, the purpose of the present invention is to provide a superlubricating gel with antibacterial function and its preparation method, covalently grafting the water-soluble superlubricating molecule polyvinylpyrrolidone onto the macromolecular chain of gelatin with carbon-carbon double bonds, and at the same time connecting the polyvinylpyrrolidone macromolecular chains into a network structure through N,N'-methylenebisacrylamide molecules to prevent the water-soluble superlubricating molecule polyvinylpyrrolidone from dissolving and losing in water, so as to achieve the purpose of long-term lubrication and drag reduction; in addition, through the reaction of the epoxy group in 2,3-epoxypropyltrimethylammonium chloride molecules with gelatin molecules, gelatin quaternary ammonium salt is generated, and the quaternary ammonium salt has a good inhibitory effect on the growth of microorganisms such as Escherichia coli and Staphylococcus aureus, and synergistically realizes long-term superlubrication and drag reduction.

[0006] In order to achieve the above purpose, the present invention is realized by adopting the following technical solutions:

[0007] A superlubricating gel with antibacterial function, the raw material components thereof include: QA-GelMA, vinylpyrrolidone monomer, N,N'-methylenebisacrylamide and ammonium persulfate;

[0008] Wherein, the mass ratio of QA-GelMA to vinylpyrrolidone monomer is 1:(1-3); the mass ratio of N,N'-methylenebisacrylamide to vinylpyrrolidone monomer is (1-5):100; the mass ratio of ammonium persulfate to vinylpyrrolidone monomer is (1-3):100.

[0009] The QA-GelMA is formed by the reaction of GelMA and 2,3-epoxypropyltrimethylammonium chloride, and the mass ratio of the two is 10:(6-10);

[0010] The GelMA is formed by the reaction of gelatin and methacrylic anhydride, and the mass-volume ratio of gelatin to methacrylic anhydride is 1:(1-2), unit g:mL.

[0011] A preparation method of a superlubricating gel with antibacterial function, comprising the following steps:

[0012] (1) Weigh 4g of gelatin, add it to 100mL of PBS solution, heat to 40°C, stir for 0.5-1h to dissolve;

[0013] (2) Add 100-130mL of DMF and 4-8mL of methacrylic anhydride to step (1) in sequence, heat to 40°C-50°C, and stir for 2-4h;

[0014] (3) Load the reaction product solution in step (2) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 3-7 days, change the dialysis fluid once every 4-12 hours, and freeze-dry to obtain the gelatin derivative GelMA grafted with carbon-carbon double bonds;

[0015] (4) Weigh 1 g of GelMA, add it to 20 mL of deionized water, heat it to 40 - 60 °C, stir for 0.5 - 1 h to dissolve it.

[0016] (5) Weigh 0.6 - 1 g of 2,3 - epoxypropyl - trimethylammonium chloride, dissolve it in 5 mL of deionized water, and drop it into the solution in step (4). Stir at 60 °C - 70 °C for 8 - 12 h.

[0017] (6) Load the reaction product solution in step (5) into a dialysis bag with a molecular weight cut - off of 10,000, dialyze for 3 - 7 days, change the dialysis fluid once every 4 - 12 h, and then freeze - dry to obtain the quaternized modified gelatin derivative QA - GelMA.

[0018] (7) Weigh 1 g of QA - GelMA, add it to 20 mL of deionized water, heat it to 40 - 60 °C, stir for 0.5 - 1 h to dissolve it.

[0019] (8) Add 1 - 3 g of vinylpyrrolidone monomer, N,N'-methylenebisacrylamide, and ammonium persulfate to the solution in step (7), stir for 0.5 - 1 h to dissolve it, put it into a centrifuge and centrifuge at 5000 - 8000 rpm for 5 - 10 min to remove bubbles.

[0020] (9) Pour the solution in step (8) into a polytetrafluoroethylene mold, and heat - treat it in an oven at 60 - 80 °C for 4 - 6 h to obtain a super - lubricating gel with antibacterial function.

[0021] In step (8), the mass ratio of N,N'-methylenebisacrylamide to vinylpyrrolidone monomer is (1 - 5):100.

[0022] In step (8), the mass ratio of ammonium persulfate to vinylpyrrolidone monomer is (1 - 3):100.

[0023] A super - lubricating gel with antibacterial function is prepared by the above method.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] (1) In step 5, 2,3 - epoxypropyl - trimethylammonium chloride is grafted onto gelatin to form a gelatin quaternary ammonium salt derivative, which effectively inhibits the adhesion and proliferation of microorganisms such as Escherichia coli and Staphylococcus aureus, achieving the purpose of antibacterial synergistic enhancement of super - lubrication.

[0026] (2) Since N,N'-methylenebisacrylamide is used as a crosslinking agent in step 8, the macromolecular chains of polyvinylpyrrolidone are connected into a three-dimensional network structure, avoiding the dissolution and loss of water-soluble macromolecules. The water-soluble superlubricant molecule polyvinylpyrrolidone is covalently grafted onto the macromolecular chain of gelatin with carbon-carbon double bonds, and at the same time, the macromolecular chains of polyvinylpyrrolidone are connected into a network structure through N,N'-methylenebisacrylamide molecules, thus solving the problem of the dissolution and loss of polyvinylpyrrolidone in water.

[0027] In summary, in the present invention, the water-soluble superlubricant molecule polyvinylpyrrolidone is covalently grafted onto the macromolecular chain of gelatin with carbon-carbon double bonds, and at the same time, the macromolecular chains of polyvinylpyrrolidone are connected into a network structure through N,N'-methylenebisacrylamide molecules, thus solving the problem of the dissolution and loss of polyvinylpyrrolidone in water. In addition, quaternary ammonium salts with antibacterial functions are introduced into the superlubricating gel, effectively inhibiting the adhesion and proliferation of microorganisms such as Escherichia coli and Staphylococcus aureus, and achieving the purpose of antibacterial synergistic enhancement of superlubrication. The surface friction of the antibacterial and superlubricating gel is less than 0.5 N, and it has good application prospects in the field of drag reduction of ships and other vehicles. Detailed implementation manners

[0028] The present invention is further illustrated below with specific examples.

[0029] Example 1

[0030] The raw material components of the superlubricating gel in this example are: QA-GelMA, vinylpyrrolidone monomer, N,N'-methylenebisacrylamide, and ammonium persulfate;

[0031] Among them, the mass ratio of QA-GelMA to the vinylpyrrolidone monomer is 1:1; the mass ratio of N,N'-methylenebisacrylamide to the vinylpyrrolidone monomer is 1:100; the mass ratio of ammonium persulfate to the vinylpyrrolidone monomer is 1:100.

[0032] The QA-GelMA is formed by reacting GelMA with 2,3-epoxypropyl-trimethylammonium chloride, and the mass ratio of the two is 10:6;

[0033] The GelMA is formed by reacting gelatin with methacrylic anhydride, and the mass-volume ratio of gelatin to methacrylic anhydride is 1:1, in units of g:mL.

[0034] The preparation of the superlubricating gel with antibacterial function in this example includes the following steps:

[0035] (1) Weigh 4 g of gelatin, add it to 100 mL of PBS solution, heat to 40 °C, and stir for 0.5 h to dissolve;

[0036] (2) Add 100 mL of DMF and 4 mL of methacrylic anhydride to step (1) in sequence, heat to 40 °C, and stir for 2 h;

[0037] (3) Load the reaction product solution in step (2) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 3 d, change the dialysis fluid once every 4 h, and freeze-dry to obtain a gelatin derivative grafted with carbon-carbon double bonds (GelMA);

[0038] (4) Weigh 1 g of GelMA, add it to 20 mL of deionized water, heat to 40 °C, and stir for 0.5 h to dissolve;

[0039] (5) Weigh 0.6 g of 2,3-epoxypropyltrimethylammonium chloride, dissolve it in 5 mL of deionized water, and drop it into the solution in step (4) above. Stir at 60 °C for 8 h;

[0040] (6) Load the reaction product solution in step (5) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 3 d, change the dialysis fluid once every 4 h, and freeze-dry to obtain a quaternized modified gelatin derivative (QA-GelMA);

[0041] (7) Weigh 1 g of QA-GelMA, add it to 20 mL of deionized water, heat to 40 °C, and stir for 0.5 h to dissolve;

[0042] (8) Add 1 g of vinylpyrrolidone monomer, 10 mg of N,N'-methylenebisacrylamide, and 10 mg of ammonium persulfate to the solution in step (7), stir for 0.5 h to dissolve, and place it in a centrifuge for centrifugal defoaming (5000 rpm, 5 min);

[0043] (9) Pour the solution in step (8) into a polytetrafluoroethylene mold (10 cm × 10 cm × 2 mm), place it in an oven at 60 °C for heat treatment for 4 h to obtain a superlubricating gel with antibacterial function.

[0044] The surface friction force of the antibacterial superlubricating gel in this example is 0.46 N, and it has excellent inhibitory growth effects on Escherichia coli and Staphylococcus aureus, has excellent antibacterial synergistic enhanced superlubricating effect, and no bacteria colonize after being placed in water for 30 days, and the lubricating effect remains unchanged.

[0045] Example Two

[0046] The raw material components of the superlubricating gel in this example are: A-GelMA, vinylpyrrolidone monomer, N,N'-methylenebisacrylamide, and ammonium persulfate;

[0047] Among them, the mass ratio of QA-GelMA to vinyl pyrrolidone monomer is 1:2; the mass ratio of N,N'-methylenebisacrylamide to vinyl pyrrolidone monomer is 2:100; the mass ratio of ammonium persulfate to vinyl pyrrolidone monomer is 2.5:100.

[0048] The said QA-GelMA is formed by the reaction of GelMA and 2,3-epoxypropyl-trimethyl ammonium chloride, and the mass ratio of the two is 10:8;

[0049] The said GelMA is formed by the reaction of gelatin and methacrylic anhydride, and the mass-volume ratio of gelatin to methacrylic anhydride is 1:1.5, with the unit g:mL.

[0050] The preparation method of the superlubricating gel with antibacterial function in this example includes the following steps:

[0051] (1) Weigh 4 g of gelatin, add it to 100 mL of PBS solution, heat to 40 °C, stir for 45 min to dissolve;

[0052] (2) Sequentially add 120 mL of DMF and 6 mL of methacrylic anhydride to step (1), heat to 45 °C, and stir for 3 h;

[0053] (3) Load the reaction product solution in step (2) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 7 d, change the dialysis fluid once every 12 h, and freeze-dry to obtain a gelatin derivative grafted with carbon-carbon double bonds (GelMA);

[0054] (4) Weigh 1 g of GelMA, add it to 20 mL of deionized water, heat to 50 °C, stir for 45 min to dissolve;

[0055] (5) Weigh 0.8 g of 2,3-epoxypropyl-trimethyl ammonium chloride, dissolve it in 5 mL of deionized water, and drop it into the solution in step (4), at 65 °C, stir for 10 h;

[0056] (6) Load the reaction product solution in step (5) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 7 d, change the dialysis fluid once every 12 h, and freeze-dry to obtain a quaternary ammonium-modified gelatin derivative (QA-GelMA);

[0057] (7) Weigh 1 g of QA-GelMA, add it to 20 mL of deionized water, heat to 50 °C, stir for 45 min to dissolve;

[0058] (8) Add 2 g of vinyl pyrrolidone monomer, 40 mg of N,N'-methylenebisacrylamide, and 50 mg of ammonium persulfate to the solution in step (7), stir for 45 min to dissolve, and place it in a centrifuge for centrifugal defoaming (7000 rpm, 8 min);

[0059] (9) Pour the solution in step (8) into a polytetrafluoroethylene mold (10 cm × 10 cm × 2 mm), and place it in an oven at 70 °C for heat treatment for 5 h to obtain a superlubricating gel with antibacterial function.

[0060] The surface friction of the antibacterial superlubricating gel in this example is 0.42 N, and it has excellent inhibitory growth effects on Escherichia coli and Staphylococcus aureus, with excellent antibacterial synergistic enhanced superlubricating effect. After being placed in water for 30 days, there is no bacterial colonization and the lubricating effect remains unchanged.

[0061] Example Three

[0062] For the superlubricating gel in this example, its raw material components are: A-GelMA, vinylpyrrolidone monomer, N,N'-methylenebisacrylamide, and ammonium persulfate;

[0063] Among them, the mass ratio of QA-GelMA to vinylpyrrolidone monomer is 1:3; the mass ratio of N,N'-methylenebisacrylamide to vinylpyrrolidone monomer is 5:100; the mass ratio of ammonium persulfate to vinylpyrrolidone monomer is 3:100.

[0064] The said QA-GelMA is formed by the reaction of GelMA and 2,3-epoxypropyl-trimethylammonium chloride, and the mass ratio of the two is 10:10;

[0065] The said GelMA is formed by the reaction of gelatin and methacrylic anhydride, and the mass-volume ratio of gelatin to methacrylic anhydride is 1:2, with the unit of g:mL.

[0066] The preparation of the superlubricating gel with antibacterial function in this example includes the following steps:

[0067] (1) Weigh 4 g of gelatin, add it to 100 mL of PBS solution, heat to 40 °C, and stir for 1 h to dissolve;

[0068] (2) Sequentially add 130 mL of DMF and 8 mL of methacrylic anhydride to (1), heat to 50 °C, and stir for 4 h;

[0069] (3) Load the reaction product solution in step (2) into a dialysis bag with a molecular weight cut-off of 10000, dialyze for 3 d, change the dialysis fluid every 12 h, and freeze-dry to obtain a gelatin derivative (GelMA) grafted with carbon-carbon double bonds;

[0070] (4) Weigh 1 g of GelMA, add it to 20 mL of deionized water, heat to 60 °C, and stir for 1 h to dissolve;

[0071] (5) Weigh 1 g of 2,3-epoxypropyltrimethylammonium chloride, dissolve it in 5 mL of deionized water, and drop it into the solution in step (4) above. Stir at 70 °C for 12 h;

[0072] (6) Load the reaction product solution in step (5) into a dialysis bag with a molecular weight cut-off of 10,000, dialyze for 3 d, change the dialysis fluid every 12 h, and freeze-dry to obtain the quaternized modified gelatin derivative (QA-GelMA);

[0073] (7) Weigh 1 g of QA-GelMA, add it to 20 mL of deionized water, heat to 60 °C, and stir for 1 h to dissolve;

[0074] (8) Add 3 g of vinylpyrrolidone monomer, 0.15 g of N,N'-methylenebisacrylamide, and 90 mg of ammonium persulfate to the solution in step (7), stir for 1 h to dissolve, and centrifuge to remove bubbles (8000 rpm, 10 min);

[0075] (9) Pour the solution in (8) into a polytetrafluoroethylene mold (10 cm × 10 cm × 2 mm), and heat-treat it in an oven at 80 °C for 6 h to obtain a superlubricating gel with antibacterial function.

[0076] The surface friction force of the antibacterial superlubricating gel in this example is 0.45 N, and it has excellent inhibitory growth effects on Escherichia coli and Staphylococcus aureus, with excellent antibacterial synergistic enhanced superlubricating effect. After being placed in water for 30 days, there is no bacterial colonization, and the lubricating effect remains unchanged.

[0077] In summary, the principle of the present invention is manifested in: grafting the water-soluble superlubricating molecule polyvinylpyrrolidone onto the gelatin macromolecular chain containing carbon-carbon double bonds by means of covalent bonds. In addition, using N,N'-methylenebisacrylamide molecules as cross-linking agents to connect these polyvinylpyrrolidone macromolecular chains into a stable network structure. Such a structural design can effectively prevent the water-soluble superlubricating molecules from dissolving and flowing away in the water environment, so as to achieve the purpose of maintaining the lubricating and drag-reducing effect for a long time. At the same time, this structure also has the additional advantage of inhibiting the adhesion and growth of bacteria and other microorganisms, which is of extremely important significance for improving the navigation efficiency and drag-reducing effect of ships in water. Further, by reacting the epoxy group in 2,3-epoxypropyltrimethylammonium chloride molecules with gelatin molecules, a gelatin quaternary ammonium salt with antibacterial properties can be generated. This quaternary ammonium salt has a significant inhibitory growth effect on a variety of microorganisms, including Escherichia coli and Staphylococcus aureus, etc. Therefore, by using this composite material, the dual effects of long-term superlubricating drag reduction and antibacterial can be achieved, providing a new solution for related fields.

Claims

1. A super lubricating gel with antibacterial function, characterized in that: The raw material components include: QA-GelMA, vinyl pyrrolidone monomer, N,N'-methylenebisacrylamide and ammonium persulfate; The mass ratio of QA-GelMA to vinyl pyrrolidone monomer is 1:(1-3); the mass ratio of N,N'-methylenebisacrylamide to vinyl pyrrolidone monomer is (1-5):100; the mass ratio of ammonium persulfate to vinyl pyrrolidone monomer is (1-3):100; The QA-GelMA is prepared by reacting GelMA and 2,3-epoxypropyl-trimethylammonium chloride, and the mass ratio of the two is 10:(6-10); The GelMA is prepared by the reaction of gelatin and methacrylic anhydride, wherein the mass volume ratio of gelatin to methacrylic anhydride is 1:(1-2), with the unit of g:mL.

2. The super lubricating gel with antibacterial function according to claim 1, characterized in that: The raw material components are: A-GelMA, vinyl pyrrolidone monomer, N,N'-methylenebisacrylamide and ammonium persulfate; Among them, the mass ratio of QA-GelMA to vinyl pyrrolidone monomer is 1:2; the mass ratio of N,N'-methylenebisacrylamide to vinyl pyrrolidone monomer is 2:100; and the mass ratio of ammonium persulfate to vinyl pyrrolidone monomer is 2.5:

100. The QA-GelMA is prepared by reacting GelMA and 2,3-epoxypropyl-trimethylammonium chloride, with a mass ratio of 10:8; The GelMA is prepared by the reaction of gelatin and methacrylic anhydride, wherein the mass volume ratio of gelatin to methacrylic anhydride is 1:1.5, in units of g:mL.

3. A method for preparing a super lubricating gel with antibacterial function, characterized in that: The following steps are involved: (1) Weigh 4 g of gelatin, add it to 100 mL of PBS solution, heat to 40°C, and stir for 0.5-1 h to dissolve; (2) Add 100-130 mL of DMF and 4-8 mL of methacrylic anhydride to step (1), heat to 40° C.-50° C., and stir for 2-4 h; (3) placing the reaction product solution in step (2) into a dialysis bag with a molecular weight cutoff of 10,000, dialyzing for 3-7 days, replacing the dialysate every 4-12 hours, and freeze-drying to obtain a gelatin derivative GelMA grafted with a carbon-carbon double bond; (4) Weigh 1 g of GelMA, add it to 20 mL of deionized water, heat it to 40-60 °C, stir it for 0.5-1 h, and dissolve it; (5) Weigh 0.6-1 g of 2,3-epoxypropyl-trimethylammonium chloride, dissolve it in 5 mL of deionized water, and add it dropwise to the solution in step (4), stir at 60° C.-70° C. for 8-12 h; (6) placing the reaction product solution in step (5) into a dialysis bag with a molecular weight cutoff of 10,000, dialyzing for 3-7 days, replacing the dialysate every 4-12 hours, and freeze-drying to obtain a quaternary ammonium-modified gelatin derivative QA-GelMA; (7) Weigh 1 g of QA-GelMA, add it to 20 mL of deionized water, heat it to 40-60 °C, stir it for 0.5-1 h, and dissolve it; (8) Add 1-3 g of vinyl pyrrolidone monomer, N,N'-methylenebisacrylamide and ammonium persulfate to the solution of step (7), stir for 0.5-1 h to dissolve, and centrifuge at 5000-8000 rpm for 5-10 min to degas; (9) Pour the solution of step (8) into a polytetrafluoroethylene mold, place it in a 60-80° C. oven for heat treatment for 4-6 hours, and thus obtain a super-lubricating gel with antibacterial function.

4. The method for preparing a super lubricating gel with antibacterial function according to claim 3, characterized in that: In the step (8), the mass ratio of N,N'-methylenebisacrylamide to vinyl pyrrolidone monomer is (1-5):

100.

5. The method for preparing a super lubricating gel with antibacterial function according to claim 3, characterized in that: In the step (8), the mass ratio of ammonium persulfate to vinyl pyrrolidone monomer is (1-3):

100.

6. A super lubricating gel with antibacterial function, characterized in that: Prepared by the preparation method of any of claims 3 to 5 above.