Hydrogel with controllable response lubricating performance and preparation method and application thereof

Abstract

The application provides a hydrogel with controllable response lubricating performance, which is a mucin-polyvinyl alcohol hydrogel, a mucin-polyvinyl alcohol / sodium alginate hydrogel, a mucin-polyvinyl alcohol / carboxymethyl cellulose sodium hydrogel, a mucin-acrylamide hydrogel or a mucin-hydroxyethyl methacrylate hydrogel, and is obtained by preparing a mucin aqueous solution, a hydrogel precursor liquid and a forming treatment. The hydrogel with controllable response lubricating performance has a low friction coefficient and can be applied to the preparation of a soft robot.

Description

Technical Field

[0001] This invention belongs to the field of hydrogel technology, specifically relating to a hydrogel with controllable response lubrication properties, its preparation method, and its application. Background Technology

[0002] When two objects move along the tangent of their contact surfaces or tend to move relative to each other, a force exists between their contact surfaces that opposes this relative motion. This force is called friction, and the phenomenon or characteristic between the contact surfaces is called "friction." Globally, approximately 23% of energy is lost annually due to friction; therefore, reducing the harm caused by friction is of great practical significance. Reducing friction requires lubrication, which is an effective technical measure to improve the frictional state of friction pairs, thereby reducing frictional resistance and slowing down wear.

[0003] Hydrogels are water-based gels, a type of polymeric network system. They are soft, can maintain their shape, and are widely used in various fields, such as drought relief in arid regions and in cosmetics like face masks, fever-reducing patches, and analgesic patches. However, their poor friction and abrasion resistance limits their practical application in many scenarios. Therefore, developing hydrogels with lubricating properties is currently a key objective. Summary of the Invention

[0004] The problem to be solved by this invention is: a hydrogel with controllable response lubrication properties, its preparation method and application, so as to solve the problems of poor lubrication performance and narrow application range of hydrogels.

[0005] The technical solution adopted to solve the technical problem is to provide a hydrogel with controllable response lubrication performance, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel, a mucin-polyvinyl alcohol / sodium alginate hydrogel, a mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel, a mucin-acrylamide hydrogel, or a mucin-hydroxyethyl methacrylate hydrogel.

[0006] This invention also provides a method for preparing a hydrogel with controllable responsive lubrication properties, comprising the following steps:

[0007] (1) Dissolve mucin in water, then centrifuge and take the supernatant to obtain a mucin aqueous solution;

[0008] (2) Preparation of base solution; the base solution is a polyvinyl alcohol aqueous solution, a mixed solution of polyvinyl alcohol and sodium alginate, a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose, an acrylamide-mucin aqueous solution or a hydroxyethyl methacrylate-mucin aqueous solution;

[0009] (3) Preparation of hydrogel precursor solution; the hydrogel precursor solution is obtained by mixing a base solution containing polyvinyl alcohol with an aqueous solution of mucin, or by adding an initiator and a crosslinking agent to a base solution without polyvinyl alcohol;

[0010] (4) The hydrogel precursor solution is molded to obtain the final product.

[0011] Preferably, the concentration of the mucin aqueous solution is 30-90 mg / mL, the centrifugation speed is 12000 r / min, and the centrifugation time is 20 min.

[0012] Preferably, the hydrogel is a mucin-polyvinyl alcohol hydrogel, which is prepared through the following steps:

[0013] (1) Polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% is mixed with water and stirred at 98°C for 3 hours to obtain a polyvinyl alcohol aqueous solution; the concentration of the polyvinyl alcohol aqueous solution is 10 to 20 wt%.

[0014] (2) Mix polyvinyl alcohol aqueous solution and mucin aqueous solution in a volume ratio of 1:1 to obtain hydrogel precursor solution;

[0015] (3) Freeze the hydrogel precursor solution at -40℃ for 8 hours, then thaw it at 25~30℃ for 8 hours. Repeat the freeze-thaw cycle 1~3 times to obtain the product.

[0016] Preferably, the hydrogel is a mucin-polyvinyl alcohol / sodium alginate hydrogel, which is prepared through the following steps:

[0017] (1) Polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% was mixed with water and stirred at 98°C for 2 hours. Then sodium alginate was added and mixed evenly to obtain a mixed solution of polyvinyl alcohol and sodium alginate. The concentration of the mixed solution of polyvinyl alcohol and sodium alginate was 10 to 25 wt%. The mass ratio of polyvinyl alcohol to sodium alginate was 25:4.

[0018] (2) Mix the mixed solution of polyvinyl alcohol and sodium alginate with the mucin aqueous solution at a volume ratio of 1:1 to obtain the hydrogel precursor solution.

[0019] (3) Freeze the hydrogel precursor solution at -40℃ for 8 hours, then thaw it at 25~30℃ for 8 hours. Repeat the freeze-thaw cycle 1~3 times to obtain the product.

[0020] Preferably, the hydrogel is a mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel, which is prepared by the following steps:

[0021] (1) Polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% was mixed with water and stirred at 98°C for 3 hours. Then sodium carboxymethyl cellulose was added and mixed evenly to obtain a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose. The concentration of the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose was 10 to 25 wt%. The mass ratio of polyvinyl alcohol to sodium carboxymethyl cellulose was 25:4.

[0022] (2) Mix a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose with an aqueous solution of mucin at a volume ratio of 1:1 to obtain a hydrogel precursor solution.

[0023] (3) Freeze the hydrogel precursor solution at -40℃ for 8 hours, then thaw it at 25~30℃ for 8 hours. Repeat the freeze-thaw cycle 1~3 times to obtain the product.

[0024] Preferably, the hydrogel is a mucin-acrylamide hydrogel, which is prepared through the following steps:

[0025] (1) Dissolve acrylamide in an aqueous solution of mucin to obtain an acrylamide-mucin aqueous solution; the concentration of the acrylamide-mucin aqueous solution is 15-20 wt%; the mass ratio of acrylamide to mucin is 25:3-9;

[0026] (2) Add cross-linking agent and initiator sequentially to acrylamide-mucin aqueous solution, stir to dissolve, and obtain hydrogel precursor solution; the amount of initiator and cross-linking agent added is 1% of the mass of acrylamide;

[0027] (3) The hydrogel precursor solution is placed at 50°C for 6 hours to obtain the product.

[0028] Preferably, the hydrogel is a mucin-hydroxyethyl methacrylate hydrogel, which is prepared through the following steps:

[0029] (1) Dissolve hydroxyethyl methacrylate in an aqueous solution of mucin to obtain an aqueous solution of hydroxyethyl methacrylate-mucin; the concentration of the aqueous solution of hydroxyethyl methacrylate-mucin is 30-45 wt%; the mass ratio of hydroxyethyl methacrylate to mucin is 667:30-90;

[0030] (2) Add cross-linking agent and initiator sequentially to hydroxyethyl methacrylate-mucin aqueous solution, stir to dissolve, and obtain hydrogel precursor solution; the amount of initiator and cross-linking agent added is 1% of the mass of hydroxyethyl methacrylate.

[0031] (3) The hydrogel precursor solution is reacted at 25-30℃ for 6 hours to obtain the product.

[0032] Preferably, the crosslinking agent is N,N-methylenebisacrylamide and the initiator is ammonium persulfate.

[0033] This invention also provides an application of hydrogels with controllable response lubrication properties in the fabrication of soft robots.

[0034] The present invention has the following beneficial effects:

[0035] (1) The hydrogel with controllable response lubrication properties prepared by the present invention can effectively reduce the coefficient of friction, has excellent lubrication properties, and can achieve friction regulation under the action of tannic acid.

[0036] (2) The hydrogel prepared by this invention is non-toxic and harmless, has good biocompatibility, and is suitable for multi-functional and multi-scenario applications;

[0037] (3) Hydrogel raw materials are cheap and readily available, and the synthesis steps are simple, making them suitable for industrial production. Attached Figure Description

[0038] Figure 1 This is a comparison chart of the coefficients of friction (COF) of mucin-polyvinyl alcohol / sodium alginate hydrogel, mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel, polyvinyl alcohol / sodium alginate hydrogel, and polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel.

[0039] Figure 2 This is a comparison chart of the coefficients of friction (COF) of mucin-acrylamide hydrogel, mucin-hydroxyethyl methacrylate hydrogel, acrylamide hydrogel, and hydroxyethyl methacrylate hydrogel.

[0040] Figure 3 This is a comparison chart of the coefficient of friction (COF) of mucin-polyvinyl alcohol hydrogels treated with different concentrations of tannic acid aqueous solution. Detailed Implementation

[0041] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0042] Example 1

[0043] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0044] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0045] (1) Weigh 0.3g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 30mg / mL.

[0046] (2) Mix 2.5g of polyvinyl alcohol (PVA) with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0047] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0048] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 28℃ for 8h. This freeze-thaw cycle was repeated 3 times to obtain the mucin-polyvinyl alcohol hydrogel.

[0049] Example 2

[0050] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0051] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0052] (1) Weigh 0.6g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 60mg / mL.

[0053] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0054] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0055] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 25℃ for 8h. This freeze-thaw cycle was repeated 3 times to obtain the mucin-polyvinyl alcohol hydrogel.

[0056] Example 3

[0057] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0058] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0059] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0060] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0061] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0062] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 30℃ for 8h. This freeze-thaw cycle was repeated 3 times to obtain the mucin-polyvinyl alcohol hydrogel.

[0063] Example 4

[0064] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0065] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0066] (1) Weigh 0.3g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 30mg / mL.

[0067] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0068] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0069] (4) Place the hydrogel precursor solution into a template with D=35mm and H=2.4mm, then freeze it in a freezer at -40℃ for 8h, then take it out and thaw it at 30℃ for 8h. Repeat this freeze-thaw cycle once to obtain mucin-polyvinyl alcohol hydrogel.

[0070] Example 5

[0071] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0072] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0073] (1) Weigh 0.3g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 30mg / mL.

[0074] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0075] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0076] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 30℃ for 8h. This freeze-thaw cycle was repeated twice to obtain the mucin-polyvinyl alcohol hydrogel.

[0077] Example 6

[0078] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0079] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0080] (1) Weigh 0.6g of mucin and dissolve it in 10mL of deionized water. Stir it with a magnetic force to completely dissolve it. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 60mg / mL.

[0081] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0082] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0083] (4) Place the hydrogel precursor solution into a template with D=35mm and H=2.4mm, then freeze it in a freezer at -40℃ for 8h, then take it out and thaw it at 30℃ for 8h. Repeat this freeze-thaw cycle once to obtain mucin-polyvinyl alcohol hydrogel.

[0084] Example 7

[0085] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0086] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0087] (1) Weigh 0.6g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 60mg / mL.

[0088] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0089] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0090] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 30℃ for 8h. This freeze-thaw cycle was repeated twice to obtain the mucin-polyvinyl alcohol hydrogel.

[0091] Example 8

[0092] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0093] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0094] (1) Weigh 0.6g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 60mg / mL.

[0095] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0096] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0097] (4) Place the hydrogel precursor solution into a template with D=35mm and H=2.4mm, then freeze it in a freezer at -40℃ for 8h, then take it out and thaw it at 30℃ for 8h. Repeat this freeze-thaw cycle once to obtain mucin-polyvinyl alcohol hydrogel.

[0098] Example 9

[0099] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol hydrogel.

[0100] The mucin-polyvinyl alcohol hydrogel in this embodiment was prepared through the following steps:

[0101] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0102] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water and heat to 98°C and stir magnetically for 3h to obtain a polyvinyl alcohol aqueous solution with a concentration of 20wt%.

[0103] (3) Take 5 mL of polyvinyl alcohol aqueous solution and place it in a beaker. Stir and add 5 mL of mucin aqueous solution. Mix well to obtain hydrogel precursor solution.

[0104] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then frozen in a freezer at -40℃ for 8h. After that, it was taken out and thawed at 30℃ for 8h. This freeze-thaw cycle was repeated twice to obtain the mucin-polyvinyl alcohol hydrogel.

[0105] Example 10

[0106] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol / sodium alginate hydrogel.

[0107] The mucin-polyvinyl alcohol / sodium alginate hydrogel in this embodiment was prepared through the following steps:

[0108] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0109] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water, heat to 98℃ and stir magnetically for 2h, then add 0.4g of sodium alginate (SA) and stir to mix evenly to obtain a mixed solution of polyvinyl alcohol and sodium alginate with a concentration of 22.48wt%.

[0110] (3) Take 5 mL of the mixed solution of polyvinyl alcohol and sodium alginate and place it in a beaker. Stir and add 5 mL of mucin aqueous solution to make the mixed solution of polyvinyl alcohol and sodium alginate and the mucin aqueous solution evenly mixed to obtain the hydrogel precursor solution.

[0111] (4) The hydrogel precursor solution was placed in a template with D=35mm and H=2.4mm, and then frozen in a refrigerator at -40℃ for 8h, and then thawed at 30℃ for 8h. This freeze-thaw cycle was repeated 3 times to obtain mucin-polyvinyl alcohol / sodium alginate hydrogel.

[0112] Example 11

[0113] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel.

[0114] The mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel in this embodiment was prepared through the following steps:

[0115] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0116] (2) Mix 2.5g of polyvinyl alcohol with a molecular weight of 100,000 to 150,000 and a degree of alcoholysis of 99% with 10mL of deionized water, heat to 98℃ and stir magnetically for 3h, then add 0.4g of sodium carboxymethyl cellulose (CMC) and stir to mix evenly to obtain a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose with a concentration of 22.48wt%.

[0117] (3) Take 5 mL of the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose and place it in a beaker. Stir and add 5 mL of mucin aqueous solution to make the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose and the mucin aqueous solution evenly mixed to obtain the hydrogel precursor solution.

[0118] (4) The hydrogel precursor solution was placed in a template with D=35mm and H=2.4mm, and then frozen in a refrigerator at -40℃ for 8h, and then thawed at 30℃ for 8h. This freeze-thaw cycle was repeated 3 times to obtain mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel.

[0119] Example 12

[0120] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-acrylamide hydrogel.

[0121] The mucin-acrylamide hydrogel in this embodiment was prepared through the following steps:

[0122] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0123] (2) Dissolve 2.5g of acrylamide (AM) in 10mL of mucin aqueous solution and stir magnetically to completely dissolve it to obtain an acrylamide-mucin aqueous solution with a concentration of 20wt%.

[0124] (3) Take 5 mL of acrylamide-mucin aqueous solution and place it in a beaker. Add 0.025 g of N,N-methylenebisacrylamide and then add 0.025 g of ammonium persulfate. Stir magnetically to dissolve it completely to obtain hydrogel precursor solution.

[0125] (4) The hydrogel precursor solution was placed into a template with D=35mm and H=2.4mm, and then placed in an oven at 50℃ for 6h to obtain mucin-acrylamide hydrogel.

[0126] Example 13

[0127] A hydrogel with controllable response lubrication properties, wherein the hydrogel is a mucin-hydroxyethyl methacrylate hydrogel.

[0128] The mucin-hydroxyethyl methacrylate hydrogel in this embodiment was prepared through the following steps:

[0129] (1) Weigh 0.9g of mucin and add it to 10mL of deionized water. Stir it with a magnetic force to dissolve it completely. Then pour the solution into a centrifuge tube and centrifuge it at 12000r / min for 20min. Take the supernatant to obtain a mucin aqueous solution with a concentration of 90mg / mL.

[0130] (2) Dissolve 6.67g of hydroxyethyl methacrylate (HEMA) in 10mL of mucin aqueous solution and stir magnetically to completely dissolve it to obtain a 40wt% hydroxyethyl methacrylate-mucin aqueous solution.

[0131] (3) Take 5 mL of hydroxyethyl methacrylate-mucin aqueous solution and place it in a beaker. Add 0.025 g of N,N-methylenebisacrylamide and then add 0.025 g of ammonium persulfate. Stir magnetically to dissolve it completely to obtain the hydrogel precursor solution.

[0132] (4) The gel precursor solution was placed into a template with D=35mm and H=2.4mm, and then reacted at 30℃ for 6h to obtain mucin-hydroxyethyl methacrylate hydrogel.

[0133] Comparative Example 1

[0134] A hydrogel, wherein the hydrogel is a polyvinyl alcohol hydrogel.

[0135] The preparation process of the polyvinyl alcohol hydrogel in this embodiment differs from that in Example 3 in that step (2) is omitted, and the mucin aqueous solution in step (4) is replaced with an equal amount of deionized water. The remaining steps are the same as in Example 3.

[0136] Comparative Example 2

[0137] A hydrogel, wherein the hydrogel is a polyvinyl alcohol / sodium alginate hydrogel.

[0138] The preparation process of the polyvinyl alcohol / sodium alginate hydrogel in this embodiment differs from that in Example 10 in that step (2) is omitted, and the mucin aqueous solution in step (4) is replaced with an equal amount of deionized water. The remaining steps are the same as in Example 10.

[0139] Comparative Example 3

[0140] A hydrogel, wherein the hydrogel is a polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel.

[0141] The preparation process of the polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel in this embodiment differs from that in Example 11 in that step (2) is omitted, and the mucin aqueous solution in step (4) is replaced with an equal amount of deionized water. The remaining steps are the same as in Example 11.

[0142] Comparative Example 4

[0143] A hydrogel, wherein the hydrogel is an acrylamide hydrogel.

[0144] The preparation process of the acrylamide hydrogel in this embodiment differs from that in Example 12 in that step (2) is omitted, and the mucin aqueous solution in step (3) is replaced with an equal amount of deionized water. The remaining steps are the same as in Example 12.

[0145] Comparative Example 5

[0146] A hydrogel, wherein the hydrogel is a hydroxyethyl methacrylate hydrogel.

[0147] The preparation process of the hydroxyethyl methacrylate hydrogel in this embodiment differs from that in Example 13 in that step (2) is omitted, and the mucin aqueous solution in step (3) is replaced with an equal amount of deionized water. The remaining steps are the same as in Example 13.

[0148] Experimental Example

[0149] 1. Test of the friction coefficient of hydrogels

[0150] Friction tests were conducted on a conventional ball-disc reciprocating tribometer (UMT-2, CETR, Bruker, USA). Under a load of 1 N, a stainless steel contact ball (6 mm in diameter) reciprocated linearly across the hydrogel surface at a shear rate of 0.5 mm / s. One reciprocating linear motion was marked as one shear cycle, with a sliding distance of 5 mm. The coefficients of friction of the hydrogels prepared in Examples 1-13 and Comparative Examples 1-5 are shown in Table 1. Figure 1 and Figure 2 .

[0151] Table 1

[0152] project coefficient of friction project coefficient of friction project coefficient of friction Example 1 0.022 Example 7 0.018 Example 13 0.026 Example 2 0.01 Example 8 0.02 Comparative Example 1 0.18 Example 3 0.008 Example 9 0.012 Comparative Example 2 0.09 Example 4 0.053 Example 10 0.021 Comparative Example 3 0.082 Example 5 0.036 Example 11 0.018 Comparative Example 4 0.32 Example 6 0.034 Example 12 0.031 Comparative Example 5 0.56

[0153] like Figure 1 As shown in Table 1, by comparing the COF values ​​of the hydrogels with responsive lubrication properties prepared in Examples 10 and 11 and Comparative Examples 2 and 3, it can be seen that the COF value of the mucin-polyvinyl alcohol / sodium alginate hydrogel is lower than that of the polyvinyl alcohol / sodium alginate hydrogel. Similarly, the COF value of the mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel is lower than that of the polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel. The results indicate that mucin has a good lubrication effect and a wide range of applications.

[0154] like Figure 2 As shown in Table 1, by comparing the COF values ​​of the hydrogels with responsive lubrication properties prepared in Examples 12 and 13 and Comparative Examples 4 and 5, it can be seen that the COF value of the mucin-acrylamide hydrogel is lower than that of the acrylamide hydrogel. Similarly, the COF value of the mucin-hydroxyethyl methacrylate hydrogel is lower than that of the hydroxyethyl methacrylate hydrogel. The results indicate that mucin has excellent lubrication effect and a wide range of applications.

[0155] 2. Friction coefficient test after treatment of mucin-polyvinyl alcohol hydrogel with tannic acid solution

[0156] Weigh 1g of tannic acid (TA) and dissolve it in 9mL of deionized water. Stir magnetically until completely dissolved to obtain a 10wt% tannic acid aqueous solution. Weigh 1.5g of tannic acid (TA) and dissolve it in 8.5mL of deionized water. Stir magnetically until completely dissolved to obtain a 15wt% tannic acid aqueous solution. Weigh 2g of tannic acid (TA) and dissolve it in 8mL of deionized water. Stir magnetically until completely dissolved to obtain a 20wt% tannic acid aqueous solution.

[0157] Mucin-polyvinyl alcohol hydrogels were treated with tannic acid aqueous solutions of concentrations of 10 wt%, 15 wt%, and 20 wt% for 1 min, respectively. The friction coefficients of the treated mucin-polyvinyl alcohol hydrogels and the untreated mucin-polyvinyl alcohol hydrogels were then measured. The results are as follows: Figure 3 As shown.

[0158] Depend on Figure 3 It can be seen that the friction coefficient of hydrogels treated with tannic acid tends to increase, and the higher the concentration of tannic acid, the greater the increase in friction coefficient. This is because the interaction between the polyphenol groups of mucin and tannic acid can cause the mucin to aggregate and precipitate, thereby achieving friction regulation.

[0159] The present invention has been described according to the above embodiments. It should be understood that the above embodiments do not limit the present invention in any way. All technical solutions obtained by equivalent substitution or equivalent transformation fall within the scope of the present invention.

Claims

1. A method for preparing a hydrogel having a controllable responsive lubricating property, characterized by, The method comprises the following steps: (1) dissolving mucin in water, then centrifuging, and taking the supernatant to obtain a mucin aqueous solution; (2) preparing a base solution; the base solution is a polyvinyl alcohol aqueous solution, a mixed solution of polyvinyl alcohol and sodium alginate, a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose, an acrylamide-mucin aqueous solution or a hydroxyethyl methacrylate-mucin aqueous solution; (3) preparing a hydrogel precursor solution; the hydrogel precursor solution is obtained by mixing the base solution containing polyvinyl alcohol with the mucin aqueous solution, or is obtained by adding an initiator and a crosslinking agent to the base solution not containing polyvinyl alcohol; (4) performing a molding treatment on the hydrogel precursor solution, and thus obtaining the mucin-polyvinyl alcohol hydrogel, the mucin-polyvinyl alcohol / sodium alginate hydrogel, the mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel, the mucin-acrylamide hydrogel or the mucin-hydroxyethyl methacrylate hydrogel. The concentration of the mucin aqueous solution is 30-90 mg / mL, the centrifugation speed is 12000 r / min, and the centrifugation time is 20 min.

2. The production method according to claim 1, characterized by: The mucin-polyvinyl alcohol hydrogel is prepared by the following steps:

3. The production method according to claim 1, wherein (1) mixing polyvinyl alcohol with a molecular weight of 100000-150000 and an alcoholysis degree of 99% with water, stirring at 98 ℃ for 3 h, and thus obtaining a polyvinyl alcohol aqueous solution; the concentration of the polyvinyl alcohol aqueous solution is 10-20 wt%; (2) mixing the polyvinyl alcohol aqueous solution with the mucin aqueous solution at a volume ratio of 1:1, and thus obtaining a hydrogel precursor solution; (3) freezing the hydrogel precursor solution at-40 ℃ for 8 h, then thawing at 25-30 ℃ for 8 h, and thus obtaining the mucin-polyvinyl alcohol hydrogel after 1-3 cycles of freezing and thawing. The mucin-polyvinyl alcohol / sodium alginate hydrogel is prepared by the following steps:

4. The production method according to claim 1, wherein (1) mixing polyvinyl alcohol with a molecular weight of 100000-150000 and an alcoholysis degree of 99% with water, stirring at 98 ℃ for 2 h, then adding sodium alginate and mixing uniformly, and thus obtaining a mixed solution of polyvinyl alcohol and sodium alginate; the concentration of the mixed solution of polyvinyl alcohol and sodium alginate is 10-25 wt%; the mass ratio of the polyvinyl alcohol to the sodium alginate is 25:4; (2) mixing the mixed solution of polyvinyl alcohol and sodium alginate with the mucin aqueous solution at a volume ratio of 1:1, and thus obtaining a hydrogel precursor solution; (3) freezing the hydrogel precursor solution at-40 ℃ for 8 h, then thawing at 25-30 ℃ for 8 h, and thus obtaining the mucin-polyvinyl alcohol / sodium alginate hydrogel after 1-3 cycles of freezing and thawing. The mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel is prepared by the following steps:

5. The production method according to claim 1, wherein (1) mixing polyvinyl alcohol with a molecular weight of 100000-150000 and an alcoholysis degree of 99% with water, stirring at 98 ℃ for 3 h, then adding sodium carboxymethyl cellulose and mixing uniformly, and thus obtaining a mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose; the concentration of the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose is 10-25 wt%; the mass ratio of the polyvinyl alcohol to the sodium carboxymethyl cellulose is 25:4; (2) mixing the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose with the mucin aqueous solution at a volume ratio of 1:1, and thus obtaining a hydrogel precursor solution; (3) freezing the hydrogel precursor solution at-40 ℃ for 8 h, then thawing at 25-30 ℃ for 8 h, and thus obtaining the mucin-polyvinyl alcohol / sodium carboxymethyl cellulose hydrogel after 1-3 cycles of freezing and thawing. (2) mixing the mixed solution of polyvinyl alcohol and sodium carboxymethyl cellulose with the mucin aqueous solution in a volume ratio of 1:1 to obtain a hydrogel precursor solution; (3) freezing the hydrogel precursor solution at-40℃ for 8h, then thawing at 25-30℃ for 8h, and repeating the freezing and thawing for 1-3 times to obtain the mucin-acrylamide hydrogel.

6. The production method according to claim 1, wherein The mucin-acrylamide hydrogel is prepared by the following steps: (1) dissolving acrylamide in a mucin aqueous solution to obtain an acrylamide-mucin aqueous solution; the concentration of the acrylamide-mucin aqueous solution is 15-20wt%; the mass ratio of acrylamide to mucin is 25:3-9; (2) adding a crosslinking agent and an initiator into the acrylamide-mucin aqueous solution in sequence, and stirring and dissolving to obtain a hydrogel precursor solution; the adding amount of the initiator and the crosslinking agent is 1% of the mass of acrylamide; (3) placing the hydrogel precursor solution at 50℃ for 6h to obtain the mucin-acrylamide hydrogel.

7. The production method according to claim 1, wherein The mucin-hydroxyethyl methacrylate hydrogel is prepared by the following steps: (1) dissolving hydroxyethyl methacrylate in a mucin aqueous solution to obtain a hydroxyethyl methacrylate-mucin aqueous solution; the concentration of the hydroxyethyl methacrylate-mucin aqueous solution is 30-45wt%; the mass ratio of hydroxyethyl methacrylate to mucin is 667:30-90; (2) adding a crosslinking agent and an initiator into the hydroxyethyl methacrylate-mucin aqueous solution in sequence, and stirring and dissolving to obtain a hydrogel precursor solution; the adding amount of the initiator and the crosslinking agent is 1% of the mass of hydroxyethyl methacrylate; (3) reacting the hydrogel precursor solution at 25-30℃ for 6h to obtain the mucin-hydroxyethyl methacrylate hydrogel.

8. The production method according to any one of claims 6 to 7, characterized by: The crosslinking agent is N,N-methylenebisacrylamide, and the initiator is ammonium persulfate.

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