Degradable luminous bionic bait and preparation method thereof
By using modified polyhydroxybutyrate and low water-soluble soy protein isolate and coating silica by sol-gel method, the problem of poor degradability of existing bionic bait materials is solved, achieving higher water resistance and corrosion resistance, suitable for large-scale applications.
Patent Information
- Application Number
- CN202411800046.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-09
- Publication Date
- 2025-02-14
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The poor degradability, insufficient water resistance and corrosion resistance of existing bionic bait materials limit their further optimization and large-scale application.
Modified polyhydroxybutyrate and low-water-soluble soy protein isolate are used as the main materials, and silica is coated by the sol-gel method to form a luminescent bionic fish bait.
It improves the biodegradability, water resistance and corrosion resistance of bionic baits, and enhances its stability and safety in water use.
Smart Images
Figure BDA0005177820300000141
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of bionic fish bait materials, and in particular to a degradable luminous bionic fish bait and a preparation method thereof. Background Art
[0002] Bionic bait materials are mainly made of flexible polymer materials such as silicone, thermoplastic elastomer (TPE) and rubber. These materials have good elasticity and softness and can accurately simulate the movement characteristics and appearance of fish. Silicone is widely used in bionic baits because of its strong corrosion resistance and excellent elasticity. In addition, the color and transparency of these materials can be customized according to the visual characteristics of different fish, increasing the bait's luring effect and showing a natural swimming posture in the water.
[0003] However, current bionic fish bait materials still face some technical challenges. First, the materials have poor biodegradability and are easily affected by the environment after use, especially in water areas where they are difficult to degrade naturally. Second, although materials such as silicone perform superiorly in some aspects, their water resistance and corrosion resistance are still insufficient. Long-term exposure to water will cause material performance to deteriorate. These technical problems limit the further optimization and large-scale application of bionic fish baits. The bionic fish baits have poor biodegradability, water resistance, and corrosion resistance, which need to be further improved.
[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention
[0005] The object of the present invention is to provide a degradable luminous bionic fish bait and a preparation method thereof, so as to solve the technical problems in the prior art that the bionic fish bait has poor degradability, and its water resistance and corrosion resistance need to be improved.
[0006] The purpose of the present invention can be achieved by the following technical scheme: A method for preparing a degradable luminous bionic fishing bait comprises the following steps:
[0007] S1. Add 100-120 parts of modified polyhydroxybutyrate, 20-30 parts of stabilizer, 3-4 parts of toughening agent, 1-2 parts of attractant, 0.8-1 parts of lubricant, and 0.1-0.5 parts of antioxidant in a three-dimensional turbine mixer, stir for 3-5 hours, put into an infrared drying oven for drying, add into an injection molding machine, melt and extrude into a molding mold to obtain a bionic fish bait matrix;
[0008] S2, coating the bionic fish bait substrate with the modified phosphorescent coating liquid, drying and curing, and obtaining a bionic fish bait with a luminescent coating.
[0009] Modified polyhydroxybutyrate reaction mechanism:
[0010] After the polyhydroxybutyrate chain segments are introduced into the side chains or end groups of the soybean protein isolate molecules, on the one hand, the polyhydroxybutyrate chain segments are adsorbed around the polar groups in the soybean protein isolate molecules, and assembled with the soybean protein isolate molecules to form a hydrophobic film layer, which prevents the diffusion and penetration of water, thereby reducing the water absorption of the soybean protein isolate molecules; on the other hand, after the polyhydroxybutyrate is copolymerized with the soybean protein isolate molecules, the hydrophobic groups of the soybean globulin are exposed to the outside, which also reduces the hydrophilicity. Under the synergistic effect of these two aspects, the water absorption of the copolymer film of soybean protein isolate and polyhydroxybutyrate is better controlled.
[0011] The introduction of polyhydroxybutyrate chain segments in copolymerization increases the irregularity of the polymer structure, which is beneficial to the biodegradation of the copolymer. Polyhydroxybutyrate is evenly dispersed in the protein, which can provide more surface area and increase the chance of contact between microorganisms and materials, thereby promoting the degradation of the entire composite material. As the copolymerization produces a small amount of cross-linked amino acid residues, the low degree of cross-linking causes a significant increase in tensile strength and yield strength, weakened strength, reduced β-folded structure, and reduced crystallinity. The synergistic effect of these effects leads to the improvement of the mechanical properties of the copolymer, which has a certain toughness and makes it easier to degrade.
[0012] Further, in step S1, the modified polyhydroxybutyrate is obtained by processing the following steps:
[0013] A1. Put low water-soluble soy protein isolate, polyhydroxybutyrate derivative and dimethyl sulfoxide solution into a reactor, raise the temperature of the reactor to 80-100°C, stir for 10-20 minutes, add sodium hydroxide solution, raise the temperature of the reactor to 110-130°C, keep warm for 3-5 hours, lower the temperature of the reactor to room temperature, filter and wash to obtain polyhydroxybutyrate copolymer;
[0014] A2. Put the polyhydroxybutyrate copolymer, phosphate buffer and acetone into an ultrasonic disperser, ultrasonically disperse for 10-20 minutes, centrifuge and perform post-treatment to obtain modified polyhydroxybutyrate.
[0015] Furthermore, in step A1, the amount ratio of the low water-soluble soy protein isolate, the polyhydroxybutyrate derivative, the dimethyl sulfoxide solution, and the sodium hydroxide solution is 200-400g:200-400g:3000-8000mL:500-800mL, and the speed of the reactor is 150-200r / min; in step A2, the amount ratio of the polyhydroxybutyrate copolymer, the phosphate buffer, and the acetone is 100-200g:300-500ml:50-80ml, the concentration of the sodium chloride solution is 0.5mol / L, and the precipitate after centrifugation is placed in a vacuum drying oven at a temperature of 80°C and dried to constant weight.
[0016] Furthermore, in step A1, the method for preparing the low water-soluble soy protein isolate is as follows: placing the soy protein isolate and deionized water into an ultrasonic disperser, ultrasonically dispersing for 5-10 minutes, adding lactic acid to adjust the pH to 5, centrifuging, dialysis, and post-treating to obtain the low water-soluble soy protein isolate.
[0017] Reaction mechanism of low water-soluble soy protein isolate:
[0018] Lactic acid can be partially dissociated into lactate ions (Lac-) and hydrogen ions (H+) in aqueous solution, which reduces the pH of the solution. Acidic conditions can promote protein hydrolysis. The hydrogen ions (H+) in lactic acid react with the peptide bonds in the protein molecules to form amino acids and small peptides to destroy the hydrogen bonds of the protein, resulting in the breaking of the peptide bonds. Hydrogen ions promote the binding of peptide bonds in the protein, especially nitrogen-containing peptide bonds, with water molecules, which are broken down into smaller peptide segments and amino acids, resulting in improved hydrophobic properties of the protein. The decomposed low water-soluble soybean protein is a large oligomer that does not contain covalent carbohydrates and has low hydrophilicity, which helps to improve the water resistance and moisture resistance of protein-based polymer materials.
[0019] Furthermore, the ratio of the soy protein isolate and deionized water is 200-400g:2000-4000mL, the molecular weight cutoff of the dialysis membrane is 10-50kDa, the lactic acid concentration is 0.1-1%, the ultrasonic dispersion speed is 4000-5000r / min, and the centrifugal separation rate is 5000r / min; the post-treatment includes placing the soy protein precipitate after centrifugal separation in a vacuum drying oven at a temperature of 50-60°C and drying to constant weight to obtain low water-soluble soy protein isolate.
[0020] Furthermore, in step A1, the polyhydroxybutyrate derivative is processed by the following steps:
[0021] B1. Put polyhydroxybutyrate and ethanol solution into an ultrasonic disperser, ultrasonically disperse for 5-10 minutes, dissolve in phosphate buffer, add methanol solution for precipitation, wash, and post-treat to obtain purified polyhydroxybutyrate;
[0022] B2, adding the purified polyhydroxybutyrate and hydrochloric acid solution into a reactor, raising the reactor temperature to 90-110°C, acid hydrolyzing for 11-13 hours, lowering the reactor temperature to room temperature, filtering, washing, dissolving in phosphate buffer, adding methanol solution for precipitation, washing, and obtaining a polyhydroxybutyrate derivative;
[0023] Further, in the step B1, the ratio of polyhydroxybutyrate, ethanol solution, phosphate buffer, and methanol solution is 100-200g:300-500mL:200-400mL:200-300mL, the ratio of 70wt% ethanol aqueous solution, phosphate buffer, and 70wt% methanol aqueous solution is 100-200g:300-500mL:200-400mL:200-300mL, the 70wt% ethanol aqueous solution is ethanol and water in an amount ratio of 70g:100mL, and the phosphate buffer is 100-200g:300-500mL:200-400mL:200-300mL. The liquid concentration is 2%, the 70wt% methanol aqueous solution is a methanol-water ratio of 70g:100mL, and the stirring rate is 500-800r / min; the post-treatment includes placing the precipitate in a vacuum drying oven at a temperature of 90-100°C and drying to constant weight to obtain purified polyhydroxybutyrate; in step B2, the purified polyhydroxybutyrate and hydrochloric acid solution are used in a ratio of 1-2g:50-100mL, the hydrochloric acid concentration is 3mol / L, the phosphate buffer concentration is 2%, the methanol concentration is 70%, and the stirring rate is 500-800r / min.
[0024] Furthermore, in step S1, the stabilizer is polyvinyl chloride, the toughening agent is polyamide, the attractant is one or more of fish powder, shrimp shell powder, earthworm powder, and coumarin, the lubricant is polytetrafluoroethylene, and the antioxidant is tert-butylhydroxyanisole; and the melt extrusion temperature of the molding machine is 180-230°C.
[0025] Further, in step S2, the modified phosphorescent coating liquid is obtained by processing the following steps:
[0026] C1. Add tetraethyl orthosilicate, anhydrous ethanol and deionized water into a constant temperature magnetic stirrer, stir for 20-30 minutes at a temperature of 60-70° C., add 0.5 wt % of dilute nitric acid, adjust the pH value of the solution to 4-4.5, and obtain a modified base liquid;
[0027] C2, adding the modified base liquid and strontium aluminate into a constant temperature magnetic stirrer, stirring for 20-30 minutes, placing in a drying oven for drying, placing in a muffle furnace for calcination, raising the temperature to 300-350°C, calcining for 4-5 hours, and obtaining a silica-coated phosphorescent powder;
[0028] C3. Put the silica-coated phosphorescent powder, high-aluminum bronze powder, acetone, xanthan gum and deionized water into a reaction kettle, stir and mix for 2-3 hours, and post-treat to obtain a modified phosphorescent coating liquid.
[0029] Reaction mechanism of modified phosphorescent coating liquid:
[0030] In the sol-gel method, the precursor of silica is hydrolyzed in an acidic or alkaline environment to generate silicic acid (Si-OH), which is further hydrolyzed and condensed to form silicon oxygen bonds (Si-O-Si), and hydrogen bonds are attached to the surface of strontium aluminate particles to form a coating layer. Finally, a thin layer of silica is deposited on the surface of strontium aluminate particles. Silica is chemically bonded to the surface of strontium aluminate. This chemical bonding can be achieved through the condensation reaction of hydroxyl groups (-OH) on the surface of strontium aluminate with silanol groups on the surface of silica to form strong silicon oxygen aluminum (Si-O-Al) chemical bonds, thereby enhancing the bonding force between the silica layer and the strontium aluminate particles, thereby improving the stability of the coating layer. This coating layer not only provides a physical barrier to protect strontium aluminate from erosion by the external environment (such as acid, alkali or high temperature), but also improves the mechanical strength, corrosion resistance and thermal stability of strontium aluminate.
[0031] Furthermore, in step C1, the amount ratio of tetraethyl orthosilicate, anhydrous ethanol, and deionized water is 100-200g:50-100g:300-500mL, the particle size of tetraethyl orthosilicate is 300 mesh, and the stirring speed is 300-400r / min; in step C2, the temperature of the drying oven is 70-80°C, and the powder is dried to a constant weight; in step C3, the amount ratio of the silica-coated phosphorescent powder, high-aluminum bronze powder, acetone, xanthan gum, and deionized water is 300-400g:200-300g:50-100mL:100-200mL:300-500mL.
[0032] The present invention has the following beneficial effects:
[0033] 1. Low water-soluble soy protein isolate is obtained by lactic acid hydrolysis. Lactic acid provides an acidic environment to promote the hydrolysis of peptide bonds in the protein, break the peptide chains into smaller molecules, reduce protein aggregation, enhance protein dispersibility, improve solubility, reduce the surface tension of soy protein, and help it disperse better in water. The main component of low water-soluble soy protein isolate has a low content of large oligomers of covalent carbohydrates, which reduces its hydrophilicity. After hydrolysis and separation, a part of the highly hydrophilic protein is further removed to improve the water resistance and moisture resistance of the protein-based polymer material.
[0034] 2. Modified polyhydroxybutyrate enhances the irregularity of the polymer structure by introducing polyhydroxybutyrate chain segments, which is beneficial to the biodegradation of the copolymer. Polyhydroxybutyrate is evenly dispersed in the protein, which can provide more surface area and increase the chance of contact between microorganisms and materials, thereby promoting the degradation of the entire composite material. As copolymerization produces a small amount of cross-linked amino acid residues, the low degree of cross-linking causes a significant increase in tensile strength and yield strength, weakened strength, reduced β-folded structure, and reduced crystallinity. The synergistic effect of these effects leads to the improvement of the mechanical properties of the copolymer, which has a certain toughness and makes it easier to degrade.
[0035] 3. Silicon dioxide is coated on the surface of strontium aluminate by the sol-gel method. Silicon oxygen bonds (Si-O-Si), hydrogen bonds and strong chemical bonds silicon oxygen aluminum (Si-O-Al) are formed through further hydrolysis and polycondensation reactions, which can enhance the binding force between the silicon dioxide layer and the strontium aluminate particles. With the increase of the amount of silicon dioxide, the coating layer can effectively slow down the fluctuation of the friction coefficient caused by the hard phase of strontium aluminate and reduce the wear rate of the composite coating. The crushed debris has a certain self-lubricating effect, which can effectively improve the luminous indication function, corrosion resistance and friction and wear performance of the composite luminescent coating of silicon dioxide coated phosphor powder prepared by explosion spraying. DETAILED DESCRIPTION
[0036] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0037] Example 1
[0038] This embodiment provides a method for preparing a degradable luminous bionic fishing bait, comprising the following steps:
[0039] S1. Preparation of low water-soluble soy protein isolate
[0040] Weigh: 200 g of soy protein isolate and 2000 mL of deionized water are put into an ultrasonic disperser, and the ultrasonic dispersion speed is 4000 r / min for 5 min. 0.1 wt % lactic acid is added to adjust the pH to 5, and the centrifugal separation rate is centrifuged at 5000 r / min. Dialysis is performed on the soy protein precipitate, and the soy protein precipitate is put into a 50 ℃ vacuum drying oven and dried to constant weight to obtain low water-soluble soy protein isolate.
[0041] S2. Purification of polyhydroxybutyrate
[0042] Weigh: 100 g of polyhydroxybutyrate, 300 mL of 70 wt% ethanol solution, and 200 mL of 2 wt% phosphate buffer, put them into an ultrasonic disperser, and ultrasonically disperse them for 5 min at a stirring rate of 500 r / min. Add 200 mL of methanol solution for precipitation, wash, and put the obtained precipitate into a vacuum drying oven at a temperature of 90-100 ° C, and dry to constant weight to obtain purified polyhydroxybutyrate.
[0043] S3, polyhydroxybutyrate derivatives
[0044] Weigh: 100 g of purified polyhydroxybutyrate and 5000 mL of 3 mol / L hydrochloric acid solution, add into a reactor, raise the reactor temperature to 90°C, acid hydrolyze for 11 hours, lower the reactor temperature to room temperature, filter, wash, dissolve in 2 wt% phosphate buffer, add 70 wt% methanol solution for precipitation, wash, and obtain a polyhydroxybutyrate derivative.
[0045] S4, polyhydroxybutyrate copolymer
[0046] Weigh: 200 g of low water-soluble soy protein isolate, 200 g of polyhydroxybutyrate derivative, and 3000 mL of dimethyl sulfoxide solution, add into the reactor, raise the temperature to 80°C, stir the reactor at a speed of 150 r / min for 10 min, add 500 mL of sodium hydroxide solution, raise the temperature of the reactor to 110°C, keep warm for 3 h, lower the temperature of the reactor to room temperature, filter, and wash to obtain a polyhydroxybutyrate copolymer.
[0047] S5, modified polyhydroxybutyrate
[0048] 100 g of polyhydroxybutyrate copolymer and 300 mL of phosphate buffer were placed in an ultrasonic disperser, ultrasonically dispersed for 10 min, and centrifuged. 50 mL of acetone was added to the precipitate for extraction. 0.5 mol / L sodium chloride solution was added, and the mixture was centrifuged and washed. The polyhydroxybutyrate copolymer precipitate was placed in a vacuum drying oven at 90 ° C and dried to constant weight to obtain modified polyhydroxybutyrate.
[0049] S6, modified base liquid
[0050] Weigh: 100 g of tetraethyl orthosilicate with a particle size of 300 mesh, 50 g of anhydrous ethanol, and 300 mL of deionized water, add them into a constant temperature magnetic stirrer, stir at a speed of 300 r / min for 20 min, the temperature is 60°C, add 0.5 wt% of dilute nitric acid, adjust the pH value of the solution to 4-4.5, and obtain a modified base liquid.
[0051] S7, Silica coated phosphor powder
[0052] Weigh: 200 mL of modified base liquid and 20 g of strontium aluminate, add into a constant temperature magnetic stirrer, stir for 20 min, put into a 70°C drying oven for drying, put into a muffle furnace for calcination, increase the temperature to 300°C, and calcine for 4 h to obtain silica-coated phosphorescent powder.
[0053] S8, modified phosphorescent coating liquid
[0054] Weigh: 300 g of silica-coated phosphorescent powder, 200 g of high-aluminum bronze powder with a particle size of 300 meshes, 50 mL of acetone, 100 mL of xanthan gum, and 300 mL of deionized water, put them into a reactor, and stir and mix for 2 hours to obtain a modified phosphorescent coating liquid.
[0055] Example 2
[0056] This embodiment provides a method for preparing a degradable luminous bionic fishing bait, comprising the following steps:
[0057] S1. Preparation of low water-soluble soy protein isolate
[0058] Weigh: 300 g of soy protein isolate and 3000 mL of deionized water are put into an ultrasonic disperser, and the ultrasonic dispersion speed is 4500 r / min for 8 min. 0.1 wt % of lactic acid is added to adjust the pH to 5, and the centrifugal separation rate is centrifuged at 5000 r / min. Dialysis is performed on the soy protein precipitate, and the soy protein precipitate is put into a 55 ℃ vacuum drying oven and dried to constant weight to obtain low water-soluble soy protein isolate.
[0059] S2. Purification of polyhydroxybutyrate
[0060] Weigh: 150 g of polyhydroxybutyrate, 400 mL of 70 wt% ethanol solution, and 300 mL of 2 wt% phosphate buffer, put them into an ultrasonic disperser, and ultrasonically disperse them for 8 min at a stirring rate of 800 r / min. Add 250 mL of methanol solution for precipitation, wash, and put the obtained precipitate into a vacuum drying oven at 95°C, and dry it to constant weight to obtain purified polyhydroxybutyrate.
[0061] S3, polyhydroxybutyrate derivatives
[0062] Weigh: 150 g of purified polyhydroxybutyrate and 8000 mL of 3 mol / L hydrochloric acid solution, add into a reactor, raise the reactor temperature to 100°C, acid hydrolyze for 12 h, lower the reactor temperature to room temperature, filter, wash, dissolve in 2 wt% phosphate buffer, add 70 wt% methanol solution for precipitation, wash, and obtain a polyhydroxybutyrate derivative.
[0063] S4, polyhydroxybutyrate copolymer
[0064] Weigh: 300 g of low water-soluble soy protein isolate, 300 g of polyhydroxybutyrate derivative, and 5000 mL of dimethyl sulfoxide solution, add into the reactor, raise the temperature to 90°C, stir the reactor at a speed of 180 r / min for 15 min, add 500 mL of sodium hydroxide solution, raise the temperature of the reactor to 120°C, keep warm for 4 hours, lower the temperature of the reactor to room temperature, filter, and wash to obtain a polyhydroxybutyrate copolymer.
[0065] S5, modified polyhydroxybutyrate
[0066] 150 g of polyhydroxybutyrate copolymer and 400 mL of phosphate buffer were placed in an ultrasonic disperser, ultrasonically dispersed for 15 min, and centrifuged. 70 mL of acetone was added to the precipitate for extraction. 0.5 mol / L sodium chloride solution was added, and the mixture was centrifuged and washed. The polyhydroxybutyrate copolymer precipitate was placed in a vacuum drying oven at 95 ° C and dried to constant weight to obtain modified polyhydroxybutyrate.
[0067] S6, modified base liquid
[0068] Weigh: 150 g of tetraethyl orthosilicate with a particle size of 300 mesh, 80 g of anhydrous ethanol, and 400 mL of deionized water, add them into a constant temperature magnetic stirrer, stir at a speed of 350 r / min for 25 min, the temperature is 65°C, add 0.5 wt% of dilute nitric acid, adjust the pH value of the solution to 4-4.5, and obtain a modified base liquid.
[0069] S7, Silica coated phosphor powder
[0070] Weigh: 250 mL of modified base liquid and 25 g of strontium aluminate, add into a constant temperature magnetic stirrer, stir for 25 min, put into a 75°C drying oven for drying, put into a muffle furnace for calcination, increase the temperature to 320°C, and calcine for 4.5 h to obtain silica-coated phosphorescent powder.
[0071] S8, modified phosphorescent coating liquid
[0072] Weigh: 350 g of silica-coated phosphorescent powder, 250 g of high-aluminum bronze powder with a particle size of 300 meshes, 70 mL of acetone, 150 mL of xanthan gum, and 400 mL of deionized water, put them into a reactor, and stir and mix for 2.5 hours to obtain a modified phosphorescent coating liquid.
[0073] Example 3
[0074] This embodiment provides a method for preparing a degradable luminous bionic fishing bait, comprising the following steps:
[0075] S1. Preparation of low water-soluble soy protein isolate
[0076] Weigh: 400 g of soy protein isolate and 4000 mL of deionized water are put into an ultrasonic disperser, and the ultrasonic dispersion speed is 5000 r / min for 10 min. 0.1 wt % of lactic acid is added to adjust the pH to 5, and the centrifugal separation rate is 5000 r / min. The soy protein precipitate is put into a 60 ℃ vacuum drying oven and dried to constant weight to obtain low water-soluble soy protein isolate.
[0077] S2. Purification of polyhydroxybutyrate
[0078] Weigh: 200 g of polyhydroxybutyrate, 500 mL of 70 wt% ethanol solution, and 400 mL of 2 wt% phosphate buffer, put them into an ultrasonic disperser, and ultrasonically disperse them at a stirring rate of 800 r / min for 10 min. Add 300 mL of methanol solution for precipitation, wash, and put the obtained precipitate into a vacuum drying oven at 100°C and dry to constant weight to obtain purified polyhydroxybutyrate.
[0079] S3, polyhydroxybutyrate derivatives
[0080] Weigh: 200 g of purified polyhydroxybutyrate and 10000 mL of 3 mol / L hydrochloric acid solution, add into a reactor, raise the reactor temperature to 110°C, acid hydrolyze for 13 h, lower the reactor temperature to room temperature, filter, wash, dissolve in 2 wt% phosphate buffer, add 70 wt% methanol solution for precipitation, wash, and obtain a polyhydroxybutyrate derivative.
[0081] S4, polyhydroxybutyrate copolymer
[0082] Weigh: 400 g of low water-soluble soy protein isolate, 400 g of polyhydroxybutyrate derivative, and 8000 mL of dimethyl sulfoxide solution, add into the reactor, raise the temperature to 80°C, stir the reactor at a speed of 200 r / min for 20 min, add 500 mL of sodium hydroxide solution, raise the temperature of the reactor to 130°C, keep warm for 5 h, lower the temperature of the reactor to room temperature, filter, and wash to obtain a polyhydroxybutyrate copolymer.
[0083] S5, modified polyhydroxybutyrate
[0084] 200 g of polyhydroxybutyrate copolymer and 500 mL of phosphate buffer were placed in an ultrasonic disperser, ultrasonically dispersed for 20 min, and centrifuged. 80 mL of acetone was added to the precipitate for extraction. 0.5 mol / L sodium chloride solution was added, and the mixture was centrifuged and washed. The polyhydroxybutyrate copolymer precipitate was placed in a vacuum drying oven at 100 ° C and dried to constant weight to obtain modified polyhydroxybutyrate.
[0085] S6, modified base liquid
[0086] Weigh: 200 g of tetraethyl orthosilicate with a particle size of 300 mesh, 100 g of anhydrous ethanol, and 500 mL of deionized water, add them into a constant temperature magnetic stirrer, stir at a speed of 400 r / min for 30 min, the temperature is 70°C, add 0.5 wt% of dilute nitric acid, adjust the pH value of the solution to 4-4.5, and obtain a modified base liquid.
[0087] S7, Silica coated phosphor powder
[0088] Weigh: 300 mL of modified base liquid and 30 g of strontium aluminate, add into a constant temperature magnetic stirrer, stir for 30 min, put into a drying oven at 80°C for drying, put into a muffle furnace for calcination, increase the temperature to 350°C, and calcine for 5 h to obtain silica-coated phosphorescent powder.
[0089] S8, modified phosphorescent coating liquid
[0090] Weigh: 400 g of silica-coated phosphorescent powder, 300 g of high-aluminum bronze powder with a particle size of 300 meshes, 100 mL of acetone, 200 mL of xanthan gum, and 500 mL of deionized water, put them into a reactor, and stir and mix for 3 hours to obtain a modified phosphorescent coating liquid.
[0091] Comparative Example 1
[0092] The difference between this comparative example and Example 3 is that in step S1, the polyhydroxybutyrate is not modified.
[0093] Comparative Example 2
[0094] The difference between this comparative example and Example 3 is that in step S1, the soybean protein is not hydrolyzed.
[0095] Comparative Example 3
[0096] The difference between this comparative example and Example 3 is that in step S2, no modification is performed on the phosphor powder.
[0097] Performance Test:
[0098] The water absorption index of plastic materials is specified in reference to the standard GB / T1034-2008 "Test for water absorption of plastics";
[0099] The degradation indicators of biodegradable plastic products are specified in reference to the standard DB46 / T505-2020 "General Technical Requirements for Fully Biodegradable Plastic Products";
[0100] Refer to the standard GB / T10654-2001 "Determination of tensile strength and elongation at break of polymer porous elastic materials" to specify the tensile strength and elongation at break of polymer materials;
[0101] Reference standard GB / T2423.17 This standard is mainly used to evaluate the corrosion resistance of coatings in salt spray environments;
[0102] Bionic bait material water absorption test, refer to the formula The method is to weigh the sample, immerse it in deionized water at room temperature (298K), take it out at a set time, wipe off the surface moisture with cotton paper, weigh it, and calculate the water absorption rate;
[0103] Reference formula for biodegradability test of bionic bait materials The method is that the sample is buried in a glass bottle filled with garden soil and degraded at 298K. The moisture content of the soil is 27%. At the set time, the sample is taken out, ultrasonically cleaned and dried, and then weighed to calculate the degradation rate Rd.
[0104] The wet tensile strength of the sample was used to evaluate the water resistance. The water resistance test of the bionic fish bait material was as follows: the sample was immersed in deionized water at 298K for 1 h, and the wet tensile strength (σH) and elongation at break (εH) were tested on an electronic universal testing machine.
[0105] Corrosion rate measurement: The layer samples were immersed in acid-base-salt solutions for 12h, 24h and 48h. The acid-base-salt solutions were selected with mass fractions of 3.5% sodium chloride solution, 5% sodium hydroxide solution and 5% sulfuric acid solution, respectively. Fluorescence micrographs of the same part of the sample under different corrosion processes were taken using a fluorescence microscope to confirm the luminescence of strontium aluminate particles in the coating and calculate the proportion of luminescent particles on the coating surface. The open circuit potential, AC impedance and polarization curve of the coating were determined using a CHI-760e electrochemical workstation to analyze the effect of silica coating amount on the corrosion resistance of the coating. The specific test results are shown in Table 1 below.
[0106] Table 1-Performance test data of the sample
[0107]
[0108] Data Analysis:
[0109] A comparative analysis of the data of Examples 1-3 and Comparative Examples 1-3 shows that the degradable luminous bionic fish bait prepared by the present invention has a water absorption rate of 9.08%, a degradation rate of 75.9%, a tensile strength of 27 MPa, an elongation at break of 15.6%, a corrosion resistance rate of 0.48%, and all performance parameters are better than those of the comparative example.
[0110] Compared with Examples 1-3, the degradation rate of Comparative Example 1 is significantly reduced, indicating that the modification of polyhydroxybutyrate makes polyhydroxybutyrate evenly dispersed in the protein, which can provide more surface area and increase the chance of contact between microorganisms and materials, thereby promoting the biodegradability of the entire composite material.
[0111] Compared with Examples 1-3, the water absorption rate of Comparative Example 2 is increased, indicating that adding lactic acid to soy protein to hydrolyze and separate and remove a portion of highly hydrophilic protein can help improve the water resistance and moisture resistance of the protein-based polymer material.
[0112] Compared with Examples 1-3, the corrosion resistance of Comparative Example 3 is increased, indicating that the modification of the phosphor powder can enhance the bonding force between the silica layer and the strontium aluminate particles. As the amount of silica increases, the coating layer can effectively slow down the fluctuation of the friction coefficient caused by the hard phase of strontium aluminate and reduce the wear rate of the composite coating.
[0113] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.
[0114] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0115] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for preparing a degradable luminous bionic fishing bait, characterized in that: The following steps are involved: S1. Add 100-120 parts of modified polyhydroxybutyrate, 20-30 parts of stabilizer, 3-4 parts of toughening agent, 1-2 parts of attractant, 0.8-1 parts of lubricant and 0.1-0.5 parts of antioxidant in a three-dimensional turbine mixer, stir for 3-5 hours, put into an infrared drying oven for drying, add into an injection molding machine, melt and extrude into a molding mold to obtain a bionic fish bait matrix; S2, coating the bionic fish bait substrate with the modified phosphorescent coating liquid, drying and curing, and obtaining a bionic fish bait with a luminescent coating.
2. The method for preparing a degradable luminous bionic fishing bait according to claim 1, characterized in that: In step S1, the modified polyhydroxybutyrate is obtained by processing the following steps: A1. Put low water-soluble soy protein isolate, polyhydroxybutyrate derivative and dimethyl sulfoxide solution into a reactor, raise the temperature of the reactor to 80-100°C, stir for 10-20 minutes, add sodium hydroxide solution, raise the temperature of the reactor to 110-130°C, keep warm for 3-5 hours, and post-treat to obtain polyhydroxybutyrate copolymer; A2. Put the polyhydroxybutyrate copolymer, phosphate buffer and acetone into an ultrasonic disperser, ultrasonically disperse for 10-20 minutes, centrifuge and perform post-treatment to obtain modified polyhydroxybutyrate.
3. The method for preparing a degradable luminous bionic fishing bait according to claim 2, characterized in that: In step A1, the amount ratio of the low water-soluble soy protein isolate, the polyhydroxybutyrate derivative, the dimethyl sulfoxide solution, and the sodium hydroxide solution is 2-4g:2-4g:30-80mL:5-8mL, and the speed of the reactor is 150-200r / min; in step A2, the amount ratio of the polyhydroxybutyrate copolymer, the phosphate buffer, and the acetone is 1-2g:3-5ml:0.5-0.8ml, and the concentration of the sodium chloride solution is 0.5mol / L.
4. The method for preparing a degradable luminous bionic fishing bait according to claim 2, characterized in that: In step A1, the method for preparing the low water-soluble soy protein isolate is as follows: placing the soy protein isolate and deionized water into an ultrasonic disperser, ultrasonically dispersing for 5-10 minutes, adding lactic acid to adjust the pH to 5, centrifuging, dialysis, and post-processing to obtain the low water-soluble soy protein isolate.
5. The method for preparing a degradable luminous bionic fishing bait according to claim 4, characterized in that: The ratio of the soy protein isolate and deionized water is 2-4 g: 20-40 mL, the molecular weight cutoff of the dialysis membrane is 10-50 kDa, the lactic acid concentration is 0.1-1%, the ultrasonic dispersion speed is 4000-5000 r / min, and the centrifugal separation speed is 5000 r / min; the post-treatment comprises placing the soy protein precipitate after centrifugal separation in a vacuum drying oven at a temperature of 50-60° C. and drying to constant weight to obtain the low water-soluble soy protein isolate.
6. The method for preparing a degradable luminous bionic fishing bait according to claim 2, characterized in that: In step A1, the polyhydroxybutyrate derivative is processed by the following steps: B1. Put polyhydroxybutyrate and ethanol solution into an ultrasonic disperser, ultrasonically disperse for 5-10 minutes, dissolve in phosphate buffer, add methanol aqueous solution for precipitation for 1-2 hours, and post-treat to obtain purified polyhydroxybutyrate; B2. Add the purified polyhydroxybutyrate and hydrochloric acid solution into a high-pressure reactor, increase the temperature of the reactor to 90-110°C, perform acid hydrolysis for 11-13 hours, and post-treat to obtain a polyhydroxybutyrate derivative.
7. The method for preparing a degradable luminous bionic fishing bait according to claim 6, characterized in that: In the step B1, the amount ratio of polyhydroxybutyrate, 70wt% ethanol aqueous solution, phosphate buffer, and 70wt% methanol aqueous solution is 100-200g:300-500mL:200-400mL:200-300mL, the 70wt% ethanol aqueous solution is ethanol, the amount ratio of water is 70g:100mL, the concentration of phosphate buffer is 2%, the 70wt% methanol aqueous solution is methanol, the amount ratio of water is 70g:100mL, and the stirring rate is 500-800r / min; post-treatment to obtain purified polyhydroxybutyrate; in step B2, the amount ratio of the purified polyhydroxybutyrate and hydrochloric acid solution is 1-2g:50-100mL, the concentration of hydrochloric acid is 3mol / L, the concentration of phosphate buffer is 2%, the concentration of methanol is 70%, and the stirring rate is 500-800r / min.
8. The method for preparing a degradable luminous bionic fishing bait according to claim 1, characterized in that: In step S1, the stabilizer is polyvinyl chloride, the toughening agent is polyamide, the attractant is one or two of fish powder, shrimp shell powder, earthworm powder, and coumarin, the lubricant is polytetrafluoroethylene, the antioxidant is tert-butyl hydroxyanisole, and the melt extrusion temperature of the molding machine is 180-230°C.
9. The method for preparing a degradable luminous bionic fishing bait according to claim 1, characterized in that: In step S2, the modified phosphorescent coating liquid is obtained by processing the following steps: C1. Add tetraethyl orthosilicate, anhydrous ethanol and deionized water into a constant temperature magnetic stirrer, stir for 20-30 minutes at a temperature of 60-70° C., add 0.5 wt % of dilute nitric acid, adjust the pH value of the solution to 4-4.5, and obtain a modified base liquid; C2, adding the modified base liquid and strontium aluminate into a constant temperature magnetic stirrer, stirring for 20-30 minutes, placing in a drying oven for drying, placing in a muffle furnace for calcination, raising the temperature to 300-350°C, calcining for 4-5 hours, and obtaining a silica-coated phosphorescent powder; C3. Put the silica-coated phosphorescent powder, high-aluminum bronze powder, acetone, xanthan gum and deionized water into a reaction kettle, stir and mix for 2-3 hours, and post-treat to obtain a modified phosphorescent coating liquid.
10. The method for preparing a degradable luminous bionic fishing bait according to claim 9, characterized in that: In step C1, the amount ratio of tetraethyl orthosilicate, anhydrous ethanol, and deionized water is 100-200g:50-100g:300-500mL, the particle size of tetraethyl orthosilicate is 300 mesh, and the stirring speed is 300-400r / min; in step C2, the amount ratio of the modified base liquid and strontium aluminate is 200-300mL:20-30g, the temperature of the drying oven is 70-80°C, and the mixture is dried to constant weight; in step C3, the amount ratio of the silica-coated phosphorescent powder, high-aluminum bronze powder, acetone, xanthan gum, and deionized water is 3-4g:2-3g:0.5-1mL:1-2mL:3-5mL, and the particle size of the high-aluminum bronze powder is 300 mesh.