A pelleted extruded yellow croaker feed and its preparation method

Abstract

This invention relates to the field of fish feed technology and discloses a pelleted extruded yellow croaker feed and its preparation method, comprising the following weight components: 30-50 parts of domestic fish meal, 2-4 parts of fish oil, 1-3 parts of seaweed powder, 12-15 parts of wheat flour, 6-10 parts of hawthorn powder, 3-5 parts of modified polylactic acid, 4-6 parts of calcium dihydrogen phosphate, 12-15 parts of compound vitamins, 0.03-0.08 parts of probiotics, and 1-3 parts of extruder. The invention involves grafting biphenyl anhydride onto polylactic acid to obtain carboxylated polylactic acid, reacting it with thionyl chloride to obtain acryloyl chloride polylactic acid, then reacting it with 5-amino-2-fluorobenzoic acid under the action of pyridine catalyst to obtain 5-amino-2-fluorobenzoic acid-grafted polylactic acid, and then reacting it with glutamic acid to obtain modified polylactic acid. The mixture is then extruded with the other raw materials, sieved, and packaged to obtain pelleted extruded yellow croaker feed.

Description

Technical Field

[0001] This invention relates to the field of fish feed technology, specifically to a pelleted extruded yellow croaker feed and its preparation method. Background Technology

[0002] Large yellow croaker is the top of my country's traditional "four major marine products" and is currently the highest-producing farmed marine fish species in my country. It is also one of my country's eight major high-quality imported aquatic products. Due to long-term artificial breeding, lack of effective breeding stock cultivation, deterioration of the breeding environment, and differences in nutritional composition between concentrated feed and natural feed, farmed large yellow croaker suffer from color degradation, reduced disease resistance, excessively high saturated fat content, and excessively low polyunsaturated fat content, which greatly affects its product value and aquaculture efficiency.

[0003] Yellow croaker is rich in protein, trace elements, and vitamins, offering excellent nutritional benefits. It is particularly beneficial for those with weak constitutions and the elderly, providing significant therapeutic effects. Yellow croaker is also rich in selenium, which helps eliminate free radicals produced during metabolism, slowing aging and offering preventative benefits against various cancers. Furthermore, yellow croaker strengthens the spleen and stomach, calms the nerves, stops diarrhea, nourishes blood, and replenishes essence. It is highly effective for iron-deficiency anemia, insomnia, dizziness, loss of appetite, and postpartum weakness in women. However, commercially available yellow croaker feed tends to settle easily and is low in protein and vitamins, failing to meet the nutritional needs of yellow croaker. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] To address the shortcomings of existing technologies, this invention provides a pelleted extruded yellow croaker feed and its preparation method, solving the problems of easy sedimentation and insufficient nutrition in the feed.

[0006] (II) Technical Solution

[0007] To achieve the above objectives, the present invention provides the following technical solution: a pelleted extruded yellow croaker feed, comprising the following weight components: 30-50 parts of domestic fish meal, 2-4 parts of fish oil, 1-3 parts of seaweed powder, 12-15 parts of wheat flour, 6-10 parts of hawthorn powder, 3-5 parts of modified polylactic acid, 4-6 parts of calcium dihydrogen phosphate, 12-15 parts of compound vitamins, 0.03-0.08 parts of probiotics, and 1-3 parts of extruder.

[0008] Preferably, the modified polylactic acid is prepared by:

[0009] (1) Polylactic acid was added to tetrahydrofuran solvent for dissolution. After the solvent was dissolved, biphenyl anhydride and stannous octoate catalyst were added. The reaction was carried out at 90-120℃ for 2-6 hours. After the reaction was completed, the solvent was removed by vacuum distillation. The product was filtered, washed and dried to obtain carboxylated polylactic acid.

[0010] (2) Add carboxylated polylactic acid to N,N-dimethylformamide solvent and mix and stir. Then add thionyl chloride and react at 70-100℃ for 4-7h. Add acetone to precipitate the precipitate. Filter the solvent, wash with deionized water and acetone in sequence, and dry to obtain polylactic acid with acryloyl chloride.

[0011] (3) Add 5-amino-2-fluorobenzoic acid to toluene solvent, stir evenly, then add acryloyl chloride polylactic acid and catalyst pyridine, react at 20-50℃ for 3-6h, after the reaction is completed, precipitate with anhydrous ethanol, filter solvent, wash with deionized water, and dry to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0012] (4) 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then glutamic acid and dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 70-120℃ for 12-22h, and the modified polylactic acid was obtained by filtration, washing and drying.

[0013] Preferably, the mass ratio of polylactic acid, biphenyl anhydride and stannous octoate catalyst in (1) is 2.1-3.2:1:0.02-0.05.

[0014] Preferably, the mass ratio of carboxylated polylactic acid to thionyl chloride in (2) is 1.4-2.5:1.

[0015] Preferably, the mass ratio of 5-amino-2-fluorobenzoic acid, acryloyl chloride polylactic acid, and catalyst pyridine in (3) is 1.4-1.8:1:0.04-0.05.

[0016] Preferably, the mass ratio of 5-amino-2-fluorobenzoic acid grafted with polylactic acid, glutamic acid and dicyclohexylcarbodiimide in (4) is 1.5-2.3:1:0.01-0.03.

[0017] Preferably, the preparation method is as follows: weigh each raw material according to the proportion, add it to a mixer and mix evenly. After stirring for 1-2 hours, take it out and add it to an extruder for extrusion. React at 60-90℃ for 2-4 hours, and the dryness is 86%-94%. The extruded material is sieved through a 150-160 mesh screen and then packaged to obtain pelleted extruded yellow croaker feed.

[0018] (III) Beneficial Technical Effects

[0019] This invention obtains carboxylated polylactic acid by grafting biphenyl anhydride onto polylactic acid, then reacts it with thionyl chloride to obtain acryloyl chloride polylactic acid, then reacts it with 5-amino-2-fluorobenzoic acid under the action of pyridine catalyst to obtain 5-amino-2-fluorobenzoic acid-grafted polylactic acid, then reacts it with glutamic acid to obtain modified polylactic acid, mixes and puffs it with various raw materials, and then sieves and packages it to obtain granular puffed yellow croaker feed.

[0020] Modified polylactic acid contains 5-amino-2-fluorobenzoic acid and glutamic acid, which have a good effect on the growth and development of yellow croaker. It works synergistically with other components in the feed to promote the growth of yellow croaker. The feed is rich in nutrients, easy to absorb, and does not easily settle. At the same time, the operation process of this invention is simple and low in cost. Attached Figure Description

[0021] Figure 1 This is a reaction circuit diagram for modified polylactic acid.

[0022] Figure 2 It refers to the settling time of the extruded yellow croaker feed. Detailed Implementation

[0023] Example 1

[0024] The raw material components in this embodiment are as follows:

[0025]

[0026]

[0027] (1) Add 2.1g of polylactic acid to tetrahydrofuran solvent for dissolution. After the solvent is dissolved, add 1g of biphenyl anhydride and 0.02g of catalyst stannous octoate. React at 90℃ for 2h. After the reaction is completed, remove the solvent by vacuum distillation, filter, wash and dry to obtain carboxylated polylactic acid.

[0028] (2) 2.8g of carboxylated polylactic acid was added to N,N-dimethylformamide solvent and mixed and stirred. Then 2g of thionyl chloride was added and reacted at 70°C for 4h. Acetone was added to precipitate the precipitate. The precipitate was filtered, washed with solvent, deionized water and acetone in sequence, and dried to obtain polylactic acid with acryloyl chloride.

[0029] (3) 1.4g of 5-amino-2-fluorobenzoic acid was added to toluene solvent, stirred evenly, and then 1g of acryloyl chloride polylactic acid and 0.04g of catalyst pyridine were added. The reaction was carried out at 20℃ for 3h. After the reaction was completed, anhydrous ethanol was precipitated, the solvent was filtered, deionized water was washed, and dried to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0030] (4) 1.5 g of 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then 1 g of glutamic acid and 0.01 g of dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 70 °C for 12 h. The mixture was filtered, washed and dried to obtain modified polylactic acid.

[0031] (5) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1 hour, take it out and add it to the extruder for extrusion. React at 60°C for 2 hours and the dryness is 86%. Sieve the extruded material through a 150-mesh sieve and then package it to obtain pelleted extruded yellow croaker feed.

[0032] Example 2

[0033] The raw material components in this embodiment are as follows:

[0034]

[0035]

[0036] (1) 6.4g of polylactic acid was added to tetrahydrofuran solvent for dissolution. After the solvent was dissolved, 2g of biphenyl anhydride and 0.1g of stannous octoate catalyst were added. The reaction was carried out at 120℃ for 6h. After the reaction was completed, the solvent was removed by vacuum distillation. The product was filtered, washed and dried to obtain carboxylated polylactic acid.

[0037] (2) 7.5g of carboxylated polylactic acid was added to N,N-dimethylformamide solvent and mixed and stirred. Then, 3g of thionyl chloride was added and reacted at 100℃ for 7h. Acetone was added to precipitate the precipitate. The precipitate was filtered, washed with solvent, deionized water and acetone in sequence, and dried to obtain polylactic acid with acryloyl chloride.

[0038] (3) 3.6g of 5-amino-2-fluorobenzoic acid was added to toluene solvent, stirred evenly, and then 2g of acryloyl chloride polylactic acid and 0.1g of catalyst pyridine were added. The reaction was carried out at 50℃ for 6h. After the reaction was completed, anhydrous ethanol was precipitated, the solvent was filtered, deionized water was washed, and dried to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0039] (4) 6.9 g of 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then 3 g of glutamic acid and 0.09 g of dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 120 °C for 22 h. The mixture was filtered, washed and dried to obtain modified polylactic acid.

[0040] (5) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 2 hours, take it out and add it to the extruder for extrusion. React at 90℃ for 4 hours and the dryness is 94%. Sieve the extruded material through a 160 mesh screen and then package it to obtain pelleted extruded yellow croaker feed.

[0041] Example 3

[0042] The raw material components in this embodiment are as follows:

[0043]

[0044]

[0045] (1) Add 4.25g of polylactic acid to tetrahydrofuran solvent for dissolution. After the solvent is dissolved, add 1.5g of biphenyl anhydride and 0.06g of catalyst stannous octoate. React at 105℃ for 4h. After the reaction is completed, remove the solvent by vacuum distillation, filter, wash and dry to obtain carboxylated polylactic acid.

[0046] (2) 5.15g of carboxylated polylactic acid was added to N,N-dimethylformamide solvent and mixed and stirred. Then 2.5g of thionyl chloride was added and reacted at 85°C for 5.5h. Acetone was added to precipitate the precipitate. The precipitate was filtered, washed with solvent, deionized water and acetone in sequence, and dried to obtain polylactic acid with acryloyl chloride.

[0047] (3) Add 2.5g of 5-amino-2-fluorobenzoic acid to toluene solvent, stir evenly, then add 1.5g of acryloyl chloride polylactic acid and 1.02g of catalyst pyridine, react at 35℃ for 4.5h, after the reaction is completed, precipitate with anhydrous ethanol, filter the solvent, wash with deionized water, and dry to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0048] (4) 4.2 g of 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then 2 g of glutamic acid and 0.05 g of dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 95 °C for 17 h, and the modified polylactic acid was obtained by filtration, washing and drying.

[0049] (5) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1.5 hours, take it out and add it to the extruder for extrusion. React at 75°C for 3 hours and the dryness is 90%. Sieve the extruded material through a 155 mesh screen and then package it to obtain pelleted extruded yellow croaker feed.

[0050] Example 4

[0051] The raw material components in this embodiment are as follows:

[0052]

[0053] (1) Add 2.1g of polylactic acid to tetrahydrofuran solvent for dissolution. After the solvent is dissolved, add 1g of biphenyl anhydride and 0.02g of catalyst stannous octoate. React at 90℃ for 2h. After the reaction is completed, remove the solvent by vacuum distillation, filter, wash and dry to obtain carboxylated polylactic acid.

[0054] (2) 7.5g of carboxylated polylactic acid was added to N,N-dimethylformamide solvent and mixed and stirred. Then, 3g of thionyl chloride was added and reacted at 100℃ for 7h. Acetone was added to precipitate the precipitate. The precipitate was filtered, washed with solvent, deionized water and acetone in sequence, and dried to obtain polylactic acid with acryloyl chloride.

[0055] (3) 3.6g of 5-amino-2-fluorobenzoic acid was added to toluene solvent, stirred evenly, and then 2g of acryloyl chloride polylactic acid and 0.1g of catalyst pyridine were added. The reaction was carried out at 50℃ for 6h. After the reaction was completed, anhydrous ethanol was precipitated, the solvent was filtered, deionized water was washed, and dried to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0056] Dissolve the mixture, then add 2g of glutamic acid and 0.05g of dicyclohexylcarbodiimide to carry out an amidation reaction. React at 95℃ for 17h, filter, wash and dry to obtain modified polylactic acid.

[0057] (5) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1.5 hours, take it out and add it to the extruder for extrusion. React at 75°C for 3 hours and the dryness is 90%. Sieve the extruded material through a 155 mesh screen and then package it to obtain pelleted extruded yellow croaker feed.

[0058] Example 5

[0059] The raw material components in this embodiment are as follows:

[0060]

[0061] (1) 6.4g of polylactic acid was added to tetrahydrofuran solvent for dissolution. After the solvent was dissolved, 2g of biphenyl anhydride and 0.1g of stannous octoate catalyst were added. The reaction was carried out at 120℃ for 6h. After the reaction was completed, the solvent was removed by vacuum distillation. The product was filtered, washed and dried to obtain carboxylated polylactic acid.

[0062] (2) 5.15g of carboxylated polylactic acid was added to N,N-dimethylformamide solvent and mixed and stirred. Then 2.5g of thionyl chloride was added and reacted at 85°C for 5.5h. Acetone was added to precipitate the precipitate. The precipitate was filtered, washed with solvent, deionized water and acetone in sequence, and dried to obtain polylactic acid with acryloyl chloride.

[0063] (3) Add 2.5g of 5-amino-2-fluorobenzoic acid to toluene solvent, stir evenly, then add 1.5g of acryloyl chloride polylactic acid and 1.02g of catalyst pyridine, react at 35℃ for 4.5h, after the reaction is completed, precipitate with anhydrous ethanol, filter the solvent, wash with deionized water, and dry to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid.

[0064] (4) 1.5 g of 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then 1 g of glutamic acid and 0.01 g of dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 70 °C for 12 h. The mixture was filtered, washed and dried to obtain modified polylactic acid.

[0065] (5) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1 hour, take it out and add it to the extruder for extrusion. React at 60°C for 2 hours and the dryness is 86%. Sieve the extruded material through a 150-mesh sieve and then package it to obtain pelleted extruded yellow croaker feed.

[0066] Comparative Example 1

[0067] The raw material components in this embodiment are as follows:

[0068]

[0069] (1) Weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1 hour, take it out and add it to the extruder for extrusion. React at 60℃ for 2 hours and the dryness is 86%. Sieve the extruded material through a 150 mesh screen and then package it to obtain pelleted extruded yellow croaker feed.

[0070] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A pelleted extruded yellow croaker feed, characterized in that, It contains the following components by weight: 30-50 parts domestic fish meal, 2-4 parts fish oil, 1-3 parts seaweed powder, 12-15 parts flour, 6-10 parts hawthorn powder, 3-5 parts modified polylactic acid, 4-6 parts calcium dihydrogen phosphate, 12-15 parts compound vitamins, 0.03-0.08 parts probiotics, and 1-3 parts leavening agent; The modified polylactic acid is prepared by: (1) Polylactic acid was added to tetrahydrofuran solvent for dissolution. After the solvent was dissolved, biphenyl anhydride and stannous octoate catalyst were added. The reaction was carried out at 90-120℃ for 2-6 hours. After the reaction was completed, the solvent was removed by vacuum distillation. The product was filtered, washed and dried to obtain carboxylated polylactic acid. (2) Add carboxylated polylactic acid to N,N-dimethylformamide solvent and mix and stir. Then add thionyl chloride and react at 70-100℃ for 4-7h. Add acetone to precipitate the precipitate. Filter the solvent, wash with deionized water and acetone in sequence, and dry to obtain polylactic acid with acryloyl chloride. (3) Add 5-amino-2-fluorobenzoic acid to toluene solvent, stir evenly, then add acryloyl chloride polylactic acid and catalyst pyridine, react at 20-50℃ for 3-6h, after the reaction is completed, precipitate with anhydrous ethanol, filter solvent, wash with deionized water, and dry to obtain 5-amino-2-fluorobenzoic acid grafted polylactic acid. (4) 5-amino-2-fluorobenzoic acid grafted polylactic acid was added to N,N-dimethylformamide solvent for dissolution, and then glutamic acid and dicyclohexylcarbodiimide were added for amidation reaction. The reaction was carried out at 70-120℃ for 12-22h, and the modified polylactic acid was obtained by filtration, washing and drying.

2. The pelleted extruded yellow croaker feed according to claim 1, characterized in that, The mass ratio of polylactic acid, biphenyl anhydride, and stannous octoate catalyst in (1) is 2.1-3.2:1:0.02-0.

05.

3. The pelleted extruded yellow croaker feed according to claim 1, characterized in that, The mass ratio of carboxylated polylactic acid to thionyl chloride in (2) is 1.4-2.5:

1.

4. The pelleted extruded yellow croaker feed according to claim 1, characterized in that, The mass ratio of 5-amino-2-fluorobenzoic acid, acryloyl chloride polylactic acid, and catalyst pyridine in (3) is 1.4-1.8:1:0.04-0.

05.

5. The pelleted extruded yellow croaker feed according to claim 1, characterized in that, In (4), the mass ratio of 5-amino-2-fluorobenzoic acid grafted with polylactic acid, glutamic acid, and dicyclohexylcarbodiimide is 1.5-2.3:1:0.01-0.

03.

6. A method for preparing pelleted extruded yellow croaker feed as described in any one of claims 1-5, characterized in that, The preparation method is as follows: weigh each raw material according to the proportion, add it to the mixer and mix evenly. After stirring for 1-2 hours, take it out and add it to the extruder for extrusion. React at 60-90℃ for 2-4 hours. The dryness is 86%-94%. The extruded material is sieved through a 150-160 mesh screen and then packaged to obtain pelleted extruded yellow croaker feed.

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