Fish slime-methacrylated gelatin hydrogel with lubrication drag reduction performance and its preparation method
By adding fish mucus to methacrylamide gelatin hydrogel and performing hydrogen bonding and photocuring crosslinking, a fish mucus-methacrylamide gelatin hydrogel with excellent anti-swelling properties and mechanical strength was prepared, which solved the problems of unstable performance and high energy consumption of existing drag reduction materials and achieved an effective drag reduction effect.
Patent Information
- Application Number
- CN202411356992.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-11-11
- Estimated Expiration
- 2044-09-27
AI Technical Summary
Existing drag-reducing materials suffer from problems such as unstable performance, high energy consumption, or difficulty in preparation in practical applications. In particular, superhydrophobic walls are prone to failure, the bubble method has high energy consumption, polymer additives are difficult to use for long-distance voyages, and methacryloyl gelatin hydrogels have weak mechanical properties and large swelling ratios.
Fish mucus-methacrylamide gelatin hydrogel was prepared by adding fish mucus to methacrylamide gelatin hydrogel and utilizing hydrogen bonding and photocuring crosslinking to form a strong three-dimensional network structure, thereby enhancing its mechanical properties and drag reduction capabilities.
The prepared hydrogel has excellent anti-swelling properties and mechanical strength, which can effectively reduce frictional resistance. It is suitable for marine drag reduction materials, extending service life and reducing energy consumption.
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Figure CN119286264B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a fish mucus-methacrylated gelatin hydrogel with lubricating and drag-reducing properties and its preparation method. Background Technology
[0002] Various resistances are generated when solids and fluids move relative to each other. The oil delivery rate of oil pipelines significantly impacts our production and daily lives; insufficient oil delivery can lead to severe economic losses. Increasing the delivery rate of oil pipelines reduces friction between the pipeline and crude oil / condensate, thereby greatly increasing the delivery volume and extending the pipeline's service life. Ships experience frictional resistance when navigating water. Studies have shown that reducing this resistance by 10% can increase both speed and distance traveled by 3.57%, improving long-distance navigation capabilities and reducing energy consumption. Therefore, it is necessary to find high-performance drag-reducing materials.
[0003] Many methods for reducing fluid drag have been proposed, including superhydrophobic drag reduction, flexible wall methods, bubble methods, polymer additive methods, and trench methods. However, superhydrophobic walls easily lose their superhydrophobic properties in practical applications, thus losing their drag-reduction effect. Bubble methods require additional energy to generate bubbles, and polymer additives are difficult to use for drag reduction in long-distance shipping. Trench methods are challenging to prepare trench structures of specific shapes. Flexible walls can effectively absorb turbulent kinetic energy through elastic deformation and release it through rebound, suppressing pressure pulses in the fluid, slowing the transition from laminar to turbulent flow in the boundary layer, and improving boundary layer stability to achieve drag reduction. Polyurea elastomers are commonly used for drag reduction in flexible walls, but their preparation requires high temperature and high pressure. Hydrogel flexible walls, as drag-reduction materials, can be applied in medical devices, artificial cartilage, coatings, and other fields. Methacrylamide gelatin hydrogels can be prepared quickly through photocrosslinking, which is simple to operate; however, methacrylamide gelatin has weak mechanical properties and a large swelling rate in water.
[0004] Therefore, it is of great significance to prepare a suitable hydrogel flexible wall drag reduction material. Summary of the Invention
[0005] The purpose of this invention is to provide a fish mucus-methacrylated gelatin hydrogel with lubricating and drag-reducing properties and its preparation method. The fish mucus-methacrylated gelatin hydrogel of this invention exhibits good anti-swelling properties, mechanical strength, and drag-reducing properties. This invention improves the mechanical properties and anti-swelling ability of the methacrylated gelatin hydrogel by adding fish mucus to it.
[0006] The fish mucus-methacrylamide gel hydrogel of the present invention with lubricating and drag-reducing properties is prepared by utilizing the hydrogen bonding interaction between the freeze-dried fish mucus (MC) and the methacrylamide gel hydrogel GelMA precursor, and the photocuring crosslinking between the GelMA precursor and polyethylene glycol diacrylate (PEGDA). The fish mucus can be firmly bound in the three-dimensional network of the hydrogel without being lost, which is beneficial for long-term drag reduction.
[0007] The preparation method is as follows: extract mucus from fish (such as loach), centrifuge, and freeze-dry to obtain MC. Dissolve gelatin (Gel) in PBS buffer, heat and stir to dissolve, add DMF, add methacrylic anhydride (MA) dropwise, stir at 40℃ for 4 hours, add ethanol to precipitate the product, centrifuge, dialyze for 3 days, and freeze-dry to obtain the GelMA precursor lyophilized product. Dissolve the GelMA precursor lyophilized product in deionized water, stir at 40℃ until dissolved, add PEGDA, MC, and (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone)I2959 photoinitiator, and photocrosslink under UV light at 365nm to obtain mucus-methacrylamide gelatin hydrogel (MC-GelMA).
[0008] Specifically:
[0009] 1) The collected fish mucus was centrifuged at 3000 r / min for 5 min. After centrifugation, the upper air bubbles and the lower precipitate were removed, and the intermediate clear liquid was freeze-dried to obtain MC.
[0010] 2) Dissolve Gel in 1×PBS, heat to 40℃ and stir until homogeneous and transparent, add DMF, add MA dropwise, heat to 40℃ and continue stirring for 4h, add ethanol to precipitate the product, put the precipitate into a centrifuge at 5000r / min for 10min, collect the precipitate and dissolve it in deionized water, dialyze at 40℃ for 3d and freeze dry to obtain the freeze-dried GelMA precursor;
[0011] 3) Dissolve the freeze-dried GelMA precursor in deionized water, heat to 40°C and stir until dissolved, add PEGDA, a certain amount of MC, and I2959 photoinitiator, introduce the solution into a tetrafluoromold, and perform photocrosslinking under ultraviolet light at 365nm to obtain MC-GelMA hydrogel.
[0012] In the above scheme, further, in step 2), the amount of Gel relative to MA is 1.25 g Gel / ml MA, at which point theoretically all the free amino groups in Gel are replaced by the amidation reaction of MA; the dropping rate of MA in step 2 is 1 ml / min; the concentration of GelMA in step 3) is 0.1 g / ml; the mass ratio of GelMA to PEGDA in step 3) is 1:1; and the concentrations of MC and I2959 photoinitiator in step 3) are 0.5–1 mg / ml and 2.5 mg / ml, respectively.
[0013] The beneficial effects of this invention are as follows:
[0014] 1. This invention uses a dosage of 1.25g Gel / ml MA to modify Gel, allowing the amino groups of Gel to be completely grafted onto MA, thereby introducing double bonds. The MA is added at a rate of 1ml / min to allow sufficient time for the Gel and MA to react, enabling them to crosslink into a covalent network under ultraviolet light. The introduction of low molecular weight PEGDA can form an interpenetrating network with GelMA to enhance the strength and mechanical properties of the hydrogel. The introduction of MC can generate hydrogen bond interactions with GelMA to enhance mechanical properties and lubrication and drag reduction capabilities.
[0015] 2. This invention uses a one-pot method to prepare GelMA, MC, and PEGDA. The preparation method is simple, but attention must be paid to the proportions of various raw materials. If the proportions are not appropriate, it will lead to a decrease in mechanical properties and drag reduction capabilities.
[0016] 3. The MC-GelMA prepared by this invention exhibits excellent drag reduction properties in epoxy resin, aluminum alloy, and glass. Simultaneously, this hydrogel possesses good mechanical strength and anti-swelling properties. It can be used as a drag reduction material for ships. Attached Figure Description
[0017] Figure 1 (a) is a schematic diagram of the preparation mechanism of GelMA, and (b) is a schematic diagram of the preparation mechanism of the fish mucus-methacrylamide gel hydrogel with lubricating and drag-reducing properties of the present invention.
[0018] Figure 2 These are the 1H NMR spectra of MA, Gel, and GelMA;
[0019] Figure 3 These are the infrared spectra of MC-GelMA3, MC, and GelMA;
[0020] Figure 4(a) shows the dissolution of loach mucus in different solutions for 10 minutes; (b) shows the dissolution of loach mucus in different solutions for 30 minutes; (c) shows the dissolution of loach mucus in different solutions for 1 hour; and (d) shows the dissolution of loach mucus in different solutions for 3 hours.
[0021] Figure 5 (a) represents the swelling rate of Gel, GelMA, MC-GelMA1, MC-GelMA2, and MC-GelMA3 in deionized water after 7 days; (b) represents the swelling rate of Gel, GelMA, MC-GelMA1, MC-GelMA2, and MC-GelMA3 in artificial seawater after 7 days; MC-GelMA1, MC-GelMA2, and MC-GelMA3 represent the concentrations of MC in step 3) as 0.5 mg / ml, 0.75 mg / ml, and 1 mg / ml, respectively.
[0022] Figure 6 These are compression curves for Gel, GelMA, and MC-GelMA3;
[0023] Figure 7 (a) is the amplitude scan diagram of Gel, GelMA, and MC-GelMA; (b) is the frequency scan diagram of Gel, GelMA, and MC-GelMA.
[0024] Figure 8 It is the coefficient of friction between plastic wrap, plastic wrap + MC, MC-GelMA and epoxy resin, aluminum alloy, and glass. Detailed Implementation
[0025] The present invention will be further described below with reference to the accompanying drawings and specific examples.
[0026] A schematic diagram illustrating the preparation mechanism of the fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties described in this invention is shown below. Figure 1 As shown, GelMA precursor is prepared by reacting MA with free amino groups in Gel via an amidation reaction. Then, the GelMA precursor is photocured and crosslinked with PEGDA and MC under UV light at 365 nm, initiating double bond formation. PEGDA acts as the crosslinking agent for photocuring, while MC undergoes hydrogen bonding reactions with its inherent amino and hydroxyl groups and the residual amino and hydroxyl groups in GelMA. These multiple synergistic effects endow the hydrogel with excellent properties; fish mucus can be firmly bound within the three-dimensional network of the hydrogel without leakage, which is beneficial for long-term drag reduction. MA, Gel, and GelMA... 1 H NMR spectra such as Figure 2 As shown, 1 appeared on GelMA. ’ 2 ’The two characteristic peaks are due to the successful grafting of MA onto the gel, introducing hydrogen atoms from the double bonds. 3 ’ These are characteristic peaks produced by unreacted amino groups in gelatin. For example... Figure 3 As shown, at 3350-3300cm -1 The peak at 1650 cm⁻¹ represents the stretching vibration of intermolecular hydrogen bonds. The enhanced absorption peak of MC-GelMA3 compared to GelMA is due to the formation of hydrogen bonds between MC and GelMA. -1 The peak at 1100 cm⁻¹ is a characteristic peak for amide groups. The absorption intensity of the MC-GelMA3 sample is greater than that of GelMA, indicating that proteins in the mucus have been successfully grafted and cross-linked onto GelMA. -1 The absorption peaks observed are generated by the stretching vibration of CO. The stretching vibration intensity of the MC-GelMA3 sample is greater than that of GelMA, indicating that the lipids in the surface mucus have been successfully grafted and cross-linked onto GelMA. This demonstrates that fish mucus has been successfully grafted and cross-linked onto GelMA. The solubility states of MC in various solutions are as follows: Figure 4 As shown, MC becomes transparent and completely dissolves in deionized water after 1 hour. MC appears as a white turbidity in acetone, dilute acid, and ethyl acetate, and forms clumps in 70% ethanol with no significant dissolution. Swelling tests are shown below. Figure 5 As shown, Gel swells to over 100% in both deionized water and artificial seawater before beginning to degrade. GelMA, MC-GelMA1, MC-GelMA2, and MC-GelMA3 all exhibit swelling rates below 25% within 7 days in both deionized water and artificial seawater. Compression tests are shown below. Figure 6 As shown, both photocuring crosslinking and the addition of MC can enhance the compressibility of the hydrogel. Rheological tests are as follows. Figure 7 As shown, strain scanning revealed that the linear viscoelastic region of the three hydrogels was between 0.01 and 0.4. Frequency scanning with a strain of 0.01 showed that their elastic modulus (G') was greater than their storage modulus (G”), and they all exhibited a gel-like structure within the frequency range. Drag reduction testing is shown below. Figure 8 As shown, both MC and GelMA can reduce the static friction coefficient, and MC-GelMA3 modified with MC has a better drag reduction effect.
[0027] Example 1:
[0028] 1) Place clean and intact loaches into a resealable bag, rub them to induce mucus secretion, collect the mucus and centrifuge at 3000 r / min for 5 min. After centrifugation, remove the upper air bubbles and the lower precipitate, and freeze-dry the clear liquid in the middle to obtain MC.
[0029] 2) Dissolve 10g of Gel in 200ml of 1×PBS, heat to 40℃ and stir until homogeneous and transparent, add 330ml of DMF, add 8ml of MA to the above solution at a rate of 1ml / min, heat to 40℃ and continue stirring for 4h, add ethanol to precipitate the product, put the precipitate into a centrifuge at 5000r / min and centrifuge for 10min, collect the precipitate and dissolve it in deionized water, dialyze at 40℃ for 3 days and then freeze dry to obtain the freeze-dried GelMA precursor;
[0030] 3) Dissolve 1g of lyophilized GelMA precursor in 10ml of deionized water, heat to 40℃ and stir until dissolved, add 1g of PEGDA, 0.005g of MC and 0.025g of I2959 photoinitiator, introduce the solution into a tetrafluoroethylene mold, and perform photocrosslinking under ultraviolet light at 365nm to obtain MC-GelMA1 hydrogel.
[0031] The MC-GelMA1 hydrogel prepared in this example had a maximum swelling rate of 23.36% in deionized water and 17.26% in artificial seawater within 7 days. This hydrogel has certain compressibility and drag reduction properties.
[0032] Example 2:
[0033] 1) Place clean and intact loaches into a resealable bag, rub them to induce mucus secretion, collect the mucus and centrifuge at 3000 r / min for 5 min. After centrifugation, remove the upper air bubbles and the lower precipitate, and freeze-dry the clear liquid in the middle to obtain MC.
[0034] 2) Dissolve 10g of Gel in 200ml of 1×PBS, heat to 40℃ and stir until homogeneous and transparent, add 330ml of DMF, add 8ml of MA to the above solution at a rate of 1ml / min, heat to 40℃ and continue stirring for 4h, add ethanol to precipitate the product, put the precipitate into a centrifuge at 5000r / min and centrifuge for 10min, collect the precipitate and dissolve it in deionized water, dialyze at 40℃ for 3 days and then freeze dry to obtain the freeze-dried GelMA precursor;
[0035] 3) Dissolve 1g of lyophilized GelMA precursor in 10ml of deionized water, heat to 40℃ and stir until dissolved, add 1g of PEGDA, 0.0075g of MC and 0.025g of I2959 photoinitiator, introduce the solution into a tetrafluoromold, and perform photocrosslinking under ultraviolet light at 365nm to obtain MC-GelMA2 hydrogel.
[0036] The MC-GelMA hydrogel prepared in this example had a maximum swelling rate of 23.26% in deionized water and 24.30% in artificial seawater within 7 days. This hydrogel has certain compressibility and drag reduction properties.
[0037] Example 3:
[0038] 1) Place clean and intact loaches into a resealable bag, rub them to induce mucus secretion, collect the mucus and centrifuge at 3000 r / min for 5 min. After centrifugation, remove the upper air bubbles and the lower precipitate, and freeze-dry the clear liquid in the middle to obtain MC.
[0039] 2) Dissolve 10g of Gel in 200ml of 1×PBS, heat to 40℃ and stir until homogeneous and transparent, add 330ml of DMF, add 8ml of MA to the above solution at a rate of 1ml / min, heat to 40℃ and continue stirring for 4h, add ethanol to precipitate the product, put the precipitate into a centrifuge at 5000r / min and centrifuge for 10min, collect the precipitate and dissolve it in deionized water, dialyze at 40℃ for 3 days and then freeze dry to obtain the freeze-dried GelMA precursor;
[0040] 3) Dissolve 1g of lyophilized GelMA precursor in 10ml of deionized water, heat to 40℃ and stir until dissolved, add 1g of PEGDA, 0.01g of MC and 0.025g of I2959 photoinitiator, introduce the solution into a tetrafluoroethylene mold, and perform photocrosslinking under ultraviolet light at 365nm to obtain MC-GelMA3 hydrogel.
[0041] The MC-GelMA hydrogel prepared in this example had a maximum swelling rate of 19.92% in deionized water and 18.58% in artificial seawater within 7 days. This hydrogel has certain compressibility and drag reduction properties.
Claims
1. A fish mucus-methacrylated gelatin hydrogel with lubricating and drag-reducing properties, characterized in that, The hydrogel utilizes the hydrogen bonding interaction between the lyophilized loach mucus and the GelMA precursor, as well as the photocuring crosslinking between the GelMA precursor and PEGDA, to achieve gelation. The hydrogel preparation method is as follows: loach mucus is extracted, centrifuged, and then freeze-dried to obtain the lyophilized loach mucus. Gelatin is dissolved in PBS buffer, heated and stirred to dissolve, DMF is added, methacrylic anhydride is added dropwise, and the mixture is stirred at 40°C for 4 hours. Ethanol is added to precipitate the product, centrifuged, dialyzed for 3 days, and then freeze-dried to obtain the lyophilized GelMA precursor. The lyophilized GelMA precursor is dissolved in deionized water and stirred at 40°C until dissolved. PEGDA, the lyophilized loach mucus, and I2959 photoinitiator are added, and the mixture is photocrosslinked under a UV lamp to obtain the fish mucus-methacrylamide gel hydrogel.
2. The method for preparing a fish mucus-methacrylamide gel hydrogel with lubricating and drag-reducing properties as described in claim 1, characterized in that, Specifically, the preparation steps include the following: 1) Centrifuge the collected loach mucus at 3000 r / min for 5 min in a centrifuge. After centrifugation, remove the upper air bubbles and the lower sediment. Take the clear liquid in the middle and freeze-dry it to obtain the freeze-dried loach mucus. 2) Dissolve gelatin in 1×PBS, heat to 40℃ and stir until homogeneous and transparent, add DMF, add methacrylic anhydride dropwise, heat to 40℃ and continue stirring for 4h, add ethanol to precipitate the product, put the precipitate into a centrifuge at 5000r / min for 10min, collect the precipitate and dissolve it in deionized water, dialyze at 40℃ for 3d and freeze-dry to obtain the freeze-dried GelMA precursor; 3) Dissolve the lyophilized GelMA precursor in deionized water, heat to 40°C and stir until dissolved, add PEGDA, lyophilized loach mucus, and I2959 photoinitiator, and perform photocrosslinking of the solution under ultraviolet light at 365nm.
3. The method for preparing fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties as described in claim 2, characterized in that, In step 2), the amount of gelatin used relative to methacrylic anhydride is 1.25 g methacrylic anhydride / ml methacrylic anhydride.
4. The method for preparing fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties as described in claim 2, characterized in that, In step 2), the methacrylic anhydride is added at a rate of 1 ml / min.
5. The method for preparing fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties as described in claim 2, characterized in that, In step 3), the concentration of GelMA is 0.1 g / ml.
6. The method for preparing fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties as described in claim 2, characterized in that, In step 3), the mass ratio of GelMA to PEGDA is 1:
1.
7. The method for preparing fish mucus-methacrylamide gelatin hydrogel with lubricating and drag-reducing properties as described in claim 2, characterized in that, In step 3), the concentrations of the freeze-dried loach mucus and the I2959 photoinitiator are 0.5~1mg / ml and 2.5mg / ml, respectively.