Biodegradable fiber and preparation method thereof

Abstract

The invention discloses a biodegradable fiber and a preparation method thereof, and relates to the field of fibers. When the biodegradable fiber is prepared, firstly, vanillin reacts with N-aminomaleimide to prepare modified vanillin; the preparation method comprises the following steps: reacting methyl trimethoxy silane with (N, N-dimethyl-3-aminopropyl) trimethoxy silane to prepare polysilsesquioxane; then adipic acid, 2, 5-furandicarboxylic acid, ethylene glycol and dimethyl (4-chlorobenzyl) phosphate are subjected to a reaction, and modified polyester is prepared; the modified vanillin, the polysilsesquioxane and the modified polyester are subjected to electrostatic spinning and then dried, and the biodegradable fiber is prepared. The biodegradable fiber prepared by the method disclosed by the invention has good mechanical properties, biodegradability, antibacterial and deodorizing properties, flame retardance and hydrophilicity.

Description

Technical Field

[0001] The invention relates to the field of fibers, in particular to a biodegradable fiber and a preparation method thereof. Background Art

[0002] Traditional plastics, represented by polyethylene, polypropylene (PP), polyvinyl chloride, etc., have been widely used in packaging materials, transportation pipelines, automobile manufacturing, aerospace and other fields due to their advantages such as low density, insulation, high specific strength, and easy processing and molding. However, traditional plastics are all petroleum-based polymers. Petroleum, as a fossil resource, is difficult to regenerate. With the shortage of petroleum resources, the cost of traditional plastics has increased. Moreover, the subsequent treatment of waste petroleum-based plastic products is very difficult. Waste plastics are difficult to reprocess and recycle. Incineration will cause air pollution. It is difficult to degrade during landfill treatment and will pollute the land, while occupying land resources.

[0003] In order to solve the above environmental problems caused by traditional petroleum-based plastics, it is urgent to seek new environmentally friendly materials that can replace traditional petroleum-based plastics. Therefore, biodegradable polymer materials have entered people's field of vision and received extensive attention in the field of scientific research. With their own advantages such as biodegradability and biocompatibility, they are widely used in various fields. Summary of the invention

[0004] The object of the present invention is to provide a biodegradable fiber and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: The invention discloses a biodegradable fiber. The biodegradable fiber is prepared by reacting vanillin with N-aminomaleimide to obtain modified vanillin; reacting methyltrimethoxysilane with (N,N-dimethyl-3-aminopropyl)trimethoxysilane to obtain polysilsesquioxane; reacting adipic acid, 2,5-furandicarboxylic acid, ethylene glycol and (4-chlorobenzyl) dimethyl phosphate to obtain modified polyester; and electrostatically spinning and drying the modified vanillin, polysilsesquioxane and modified polyester.

[0006] A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol are mixed in a mass ratio of 1: (1.3-1.7): (15-25), stirred at 400-600 r / min at 35-45°C for 3-5 h, and rotary evaporated at 40-50°C for 6-8 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:(0.2~0.4):(18~22):(3~5), and a 0.1 mol / L sodium hydroxide aqueous solution (0.05~0.15 times the mass of methyl ethyl ketone) was added dropwise at a rate of 2~4 ml / min at 0°C. After the addition was completed, the reaction was continued for 0.5~1.5 h, and the temperature was raised to 70~80°C and the reaction was continued for 22~26 h. The organic phase was extracted and washed with dichloromethane for 3~5 times, and the organic phase was taken and distilled at 50~60°C under reduced pressure for 4~6 h to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol are added to a reactor in a molar ratio of 1:1:2, nitrogen is introduced, ethylene glycol antimony in an amount of 0.0003-0.0007 times the mass of 2,5-furandicarboxylic acid is added, stirring is carried out at 180-200°C and a speed of 200-400 r / min for 1-2 hours, (4-chlorobenzyl) dimethyl phosphate in an amount of 1-1.4 times the molar number of adipic acid is added, the temperature is raised to 195-205°C and the reaction is continued. When esterification water is no longer distilled, the pressure is adjusted to 90-110 Pa within 30 minutes, the temperature is raised to 230-240°C, the speed is adjusted to 50-70 r / min and stirring is carried out until the reaction is terminated, nitrogen is introduced to restore the pressure to normal pressure, the mixture is cooled to room temperature, and the polyester material is obtained by discharging; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride and chloroform are mixed, stirred at 400-600 r / min at 55-65°C for 3-5 h, cooled to room temperature to obtain a spinning solution, and the fiber is prepared by electrospinning technology. The fiber is dried at 75-85°C for 4-6 h and cooled to room temperature to obtain a biodegradable fiber.

[0007] As an optimization, the reaction process for preparing modified vanillin in step (1) is as follows: .

[0008] As an optimization, the mass ratio of the polyester material, polysilsesquioxane, modified vanillin, aluminum chloride and chloroform in step (4) is 1: (0.2-0.4): (0.2-0.4): (0.04-0.06): (15-25).

[0009] As an optimization, the electrospinning process parameters of step (4) are: propulsion rate 0.6 ml / h, voltage 23 kV, receiving distance 12 cm, and ambient humidity 40-50%.

[0010] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the biodegradable fiber, the present invention comprises the following steps: reacting vanillin with N-aminomaleimide to obtain modified vanillin; reacting methyltrimethoxysilane with (N,N-dimethyl-3-aminopropyl)trimethoxysilane to obtain polysilsesquioxane; reacting adipic acid, 2,5-furandicarboxylic acid, ethylene glycol with (4-chlorobenzyl) dimethyl phosphate to obtain modified polyester; and subjecting the modified vanillin, polysilsesquioxane and modified polyester to electrostatic spinning and drying to obtain the biodegradable fiber.

[0011] Firstly, vanillin is reacted with N-aminomaleimide to obtain modified vanillin. The phenolic hydroxyl structure of vanillin can react with ammonia to make the fiber have deodorizing properties, and the conjugated structure of maleimide can undergo a cyclization reaction with the furan structure on the polyester material to improve the cross-linking effect of the modified vanillin and the polyester material, thereby making the deodorizing property of the biodegradable fiber more durable and improving the mechanical properties of the fiber; adipic acid, 2,5-furandicarboxylic acid, ethylene glycol and (4-chlorobenzyl) dimethyl phosphate are reacted to obtain modified polyester, wherein (4-chlorobenzyl) dimethyl phosphate introduces phosphorus, thereby improving the flame retardant properties of the fiber.

[0012] Secondly, the polysilsesquioxane prepared by the reaction of methyltrimethoxysilane and (N,N-dimethyl-3-aminopropyl)trimethoxysilane has a cage structure, which can effectively improve the mechanical properties of the fiber. The tertiary amine on the (N,N-dimethyl-3-aminopropyl)trimethoxysilane reacts with the polyester material to form a quaternary ammonium salt. The quaternary ammonium salt acts as a cationic antibacterial agent. On the one hand, it improves the antibacterial properties of the fiber. On the other hand, the polysilsesquioxane forms a stable crosslink with the polyester fiber, which improves the mechanical properties of the fiber. The quaternary ammonium salt acts as a hydrophilic group and can improve the hydrophilicity of the fiber. DETAILED DESCRIPTION

[0013] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Example 1

[0014] A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.3:15, stirred at 400 r / min at 35°C for 3 h, and rotary evaporated at 40°C for 6 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:0.2:18:3, and a 0.1 mol / L sodium hydroxide aqueous solution (0.05 times the mass of methyl ethyl ketone) was added dropwise at a rate of 2 ml / min at 0°C. After the addition was completed, the reaction was continued for 0.5-1.5 h, and the temperature was raised to 70°C and the reaction was continued for 22 h. The organic phase was extracted and washed with dichloromethane for 3 times, and the organic phase was taken and distilled at 50°C under reduced pressure for 4 h to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, 0.0003 times the mass of 2,5-furandicarboxylic acid was added as ethylene glycol antimony, the mixture was stirred at 180°C and 200 r / min for 1 h, (4-chlorobenzyl) dimethyl phosphate was added as 1 times the molar number of adipic acid, the temperature was raised to 195°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 90 Pa within 30 min, the temperature was raised to 230°C, the speed was adjusted to 50 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.2:0.2:0.04:15, stirred at 400 r / min at 55 °C for 3 h, cooled to room temperature to obtain a spinning solution, and the fiber was prepared by electrospinning technology. The fiber was dried at 75 °C for 4 h and cooled to room temperature to obtain a biodegradable fiber.

[0015] Example 2 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.4:20, stirred at 40°C and 500 r / min for 4 h, and rotary evaporated at 45°C for 7 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:0.3:20:4, and a 0.1 mol / L sodium hydroxide aqueous solution (0.1 times the mass of methyl ethyl ketone) was added dropwise at a rate of 3 ml / min at 0°C. After the addition was completed, the reaction was continued for 1 hour, and the temperature was raised to 75°C and the reaction was continued for 24 hours. The organic phase was extracted and washed with dichloromethane for 4 times, and the organic phase was taken and distilled at 55°C under reduced pressure for 5 hours to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, ethylene glycol antimony in an amount of 0.0005 times the mass of 2,5-furandicarboxylic acid was added, the mixture was stirred at 190°C and a speed of 300 r / min for 1.5 h, (4-chlorobenzyl) dimethyl phosphate in an amount of 1.2 times the molar number of adipic acid was added, the temperature was raised to 200°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 100 Pa within 30 minutes, the temperature was raised to 235°C, the speed was adjusted to 60 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging the material; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.3:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and fibers were prepared by electrospinning technology. The fibers were dried at 80°C for 5 h, and cooled to room temperature to obtain biodegradable fibers.

[0016] Example 3 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.7:25, stirred at 45°C and 600 r / min for 5 h, and rotary evaporated at 50°C for 8 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1: 0.4:22: 5, and a 0.1 mol / L sodium hydroxide aqueous solution (0.15 times the mass of methyl ethyl ketone) was added dropwise at a rate of 4 ml / min at 0°C. After the addition was completed, the reaction was continued for 1.5 h, and the temperature was raised to 80°C and the reaction was continued for 26 h. The organic phase was extracted and washed with dichloromethane for 5 times, and the organic phase was taken and distilled at 60°C under reduced pressure for 6 h to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, ethylene glycol antimony in an amount of 0.0007 times the mass of 2,5-furandicarboxylic acid was added, the mixture was stirred at 200°C and a speed of 400 r / min for 2 h, (4-chlorobenzyl) dimethyl phosphate in an amount of 1.4 times the molar number of adipic acid was added, the temperature was raised to 205°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 110 Pa within 30 min, the temperature was raised to 240°C, the speed was adjusted to 70 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging the material; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.4:0.4:0.06:25, stirred at 65°C and 600 r / min for 5 h, cooled to room temperature to obtain a spinning solution, and fibers were prepared by electrospinning technology. The fibers were dried at 85°C for 6 h, and cooled to room temperature to obtain biodegradable fibers.

[0017] Comparative Example 1 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:0.3:20:4, and a 0.1 mol / L sodium hydroxide aqueous solution (0.1 times the mass of methyl ethyl ketone) was added dropwise at a rate of 3 ml / min at 0°C. After the addition was completed, the reaction was continued for 1 hour, and the temperature was raised to 75°C and the reaction was continued for 24 hours. The organic phase was extracted and washed with dichloromethane for 4 times, and the organic phase was taken and distilled at 55°C under reduced pressure for 5 hours to obtain polysilsesquioxane; (2) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, ethylene glycol antimony in an amount of 0.0005 times the mass of 2,5-furandicarboxylic acid was added, the mixture was stirred at 190°C and a speed of 300 r / min for 1.5 h, (4-chlorobenzyl) dimethyl phosphate in an amount of 1.2 times the molar number of adipic acid was added, the temperature was raised to 200°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 100 Pa within 30 minutes, the temperature was raised to 235°C, the speed was adjusted to 60 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging the material; (3) The polyester material, polysilsesquioxane, N-aminomaleimide, aluminum chloride and chloroform were mixed in a mass ratio of 1:0.3:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and the fiber was prepared by electrospinning technology. The fiber was dried at 80°C for 5 h and cooled to room temperature to obtain a biodegradable fiber.

[0018] Comparative Example 2 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.4:20, stirred at 40°C and 500 r / min for 4 h, and rotary evaporated at 45°C for 7 h to obtain modified vanillin; (2) Methyltrimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:20:4, and a 0.1 mol / L sodium hydroxide aqueous solution (0.1 times the mass of methyl ethyl ketone) was added dropwise at a rate of 3 ml / min at 0°C. After the addition was completed, the reaction was continued for 1 hour, and the temperature was raised to 75°C and the reaction was continued for 24 hours. The organic phase was extracted and washed with dichloromethane for 4 times, and the organic phase was taken and distilled at 55°C under reduced pressure for 5 hours to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, ethylene glycol antimony in an amount of 0.0005 times the mass of 2,5-furandicarboxylic acid was added, the mixture was stirred at 190°C and a speed of 300 r / min for 1.5 h, (4-chlorobenzyl) dimethyl phosphate in an amount of 1.2 times the molar number of adipic acid was added, the temperature was raised to 200°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 100 Pa within 30 minutes, the temperature was raised to 235°C, the speed was adjusted to 60 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging the material; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.3:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and fibers were prepared by electrospinning technology. The fibers were dried at 80°C for 5 h, and cooled to room temperature to obtain biodegradable fibers.

[0019] Comparative Example 3 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.4:20, stirred at 40°C and 500 r / min for 4 h, and rotary evaporated at 45°C for 7 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:0.3:20:4, and a 0.1 mol / L sodium hydroxide aqueous solution (0.1 times the mass of methyl ethyl ketone) was added dropwise at a rate of 3 ml / min at 0°C. After the addition was completed, the reaction was continued for 1 hour, and the temperature was raised to 75°C and the reaction was continued for 24 hours. The organic phase was extracted and washed with dichloromethane for 4 times, and the organic phase was taken and distilled at 55°C under reduced pressure for 5 hours to obtain polysilsesquioxane; (3) Add adipic acid and ethylene glycol in a molar ratio of 1:1 into a reactor, introduce nitrogen, add ethylene glycol antimony in an amount of 0.0005 times the mass of 2,5-furandicarboxylic acid, stir at 190°C and 300 r / min for 1.5 h, add (4-chlorobenzyl) dimethyl phosphate in an amount of 1.2 times the molar number of adipic acid, raise the temperature to 200°C and continue the reaction. When esterification water no longer distills out, adjust the pressure to 100 Pa within 30 min, raise the temperature to 235°C, adjust the speed to 60 r / min and stir until the reaction stops, introduce nitrogen to restore the pressure to normal pressure, cool to room temperature, and discharge to obtain a polyester material; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.3:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and fibers were prepared by electrospinning technology. The fibers were dried at 80°C for 5 h, and cooled to room temperature to obtain biodegradable fibers.

[0020] Comparative Example 4 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.4:20, stirred at 40°C and 500 r / min for 4 h, and rotary evaporated at 45°C for 7 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:0.3:20:4, and a 0.1 mol / L sodium hydroxide aqueous solution (0.1 times the mass of methyl ethyl ketone) was added dropwise at a rate of 3 ml / min at 0°C. After the addition was completed, the reaction was continued for 1 hour, and the temperature was raised to 75°C and the reaction was continued for 24 hours. The organic phase was extracted and washed with dichloromethane for 4 times, and the organic phase was taken and distilled at 55°C under reduced pressure for 5 hours to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, 0.0005 times the mass of 2,5-furandicarboxylic acid was added as ethylene glycol antimony, the mixture was stirred at 190°C and a speed of 300 r / min for 1.5 h, the temperature was raised to 200°C and the reaction was continued. When the esterification water was no longer distilled, the pressure was adjusted to 100 Pa within 30 min, the temperature was raised to 235°C, the speed was adjusted to 60 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.3:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and fibers were prepared by electrospinning technology. The fibers were dried at 80°C for 5 h, and cooled to room temperature to obtain biodegradable fibers.

[0021] Comparative Example 5 A method for preparing biodegradable fiber, comprising the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol were mixed in a mass ratio of 1:1.4:20, stirred at 40°C and 500 r / min for 4 h, and rotary evaporated at 45°C for 7 h to obtain modified vanillin; (2) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reactor in a molar ratio of 1:1:2, nitrogen was introduced, ethylene glycol antimony in an amount of 0.0005 times the mass of 2,5-furandicarboxylic acid was added, the mixture was stirred at 190°C and a speed of 300 r / min for 1.5 h, (4-chlorobenzyl) dimethyl phosphate in an amount of 1.2 times the molar number of adipic acid was added, the temperature was raised to 200°C and the reaction was continued. When the esterification water was no longer distilled out, the pressure was adjusted to 100 Pa within 30 minutes, the temperature was raised to 235°C, the speed was adjusted to 60 r / min and the mixture was stirred until the reaction was terminated, nitrogen was introduced to restore the pressure to normal pressure, the mixture was cooled to room temperature, and the polyester material was obtained by discharging the material; (3) The polyester material, modified vanillin, aluminum chloride, and chloroform were mixed in a mass ratio of 1:0.3:0.05:20, stirred at 60°C and 500 r / min for 4 h, cooled to room temperature to obtain a spinning solution, and the fiber was prepared by electrospinning technology. The fiber was dried at 80°C for 5 h and cooled to room temperature to obtain a biodegradable fiber.

[0022] Test Example 1 Flame retardant performance test: Test method: The examples and comparative examples were melted at 170°C to prepare standard specimens according to GB / T 2406.2, and the limiting oxygen index of the standard specimens was tested. The results are shown in Table 1.

[0023] Table 1

[0024] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the biodegradable fiber prepared in the present invention has good flame retardant properties.

[0025] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that the modified polyester is prepared by the reaction of adipic acid, 2,5-furandicarboxylic acid, ethylene glycol and (4-chlorobenzyl) dimethyl phosphate, wherein (4-chlorobenzyl) dimethyl phosphate introduces phosphorus, thereby improving the flame retardant properties of the fiber. Test Example 2 Deodorization performance test: Test method: The test uses MHY-14703 type spectrophotometer six-in-one indoor air detector, and the test is carried out according to the standard ISO17299-1-2014 "Determination of deodorization performance of textiles Part 1". Take 50g of each of the embodiment and the comparative example as the test sample, take 500ml of ammonia water and appropriate amount of sodium hydroxide, set the sealed environment temperature to 20℃±2℃, and the relative humidity to 60%±2%, measure 20ml of ammonia water and pour it into the test container, then put it into a sealed box, add a certain amount of sodium hydroxide, immediately close the sealed box, and measure the ammonia concentration in the sealed box after standing for 1h, then place the test sample in the sealed box, stand for 12h to fully absorb ammonia, and then measure the ammonia concentration in the sealed box to calculate the deodorization rate. The results are shown in Table 2.

[0026] Table 2

[0027] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 2, it can be found that the biodegradable fiber prepared by the present invention has good deodorizing performance.

[0028] By comparison, the deodorization rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that the phenolic hydroxyl structure of vanillin can react with ammonia to impart deodorization properties to the fiber.

[0029] Test Example 3 Mechanical properties test: Test method: The mechanical properties of the embodiment and the comparative example were tested using the XL-1A filament tensile tester. The sample was passed around the yarn guide hook and the yarn guide wheel, and passed downward through the upper and lower clamps to ensure that the sample was straightened without relaxation. A pre-tension of about 10 cN was applied to the sample. The lower clamp drove the sample downward until the sample broke and then returned to its original position to obtain the breaking strength of the sample. The clamping distance was 250 mm, the tensile speed was 250 mm / min, and each sample was repeated more than 10 times, and the test results were averaged. The results are shown in Table 3.

[0030] Table 3

[0031] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 3, it can be found that the biodegradable fiber prepared by the present invention has good mechanical properties.

[0032] By comparison, the breaking strength of Examples 1 to 3 is significantly greater than that of Comparative Example 5, indicating that the polysilsesquioxane obtained by the reaction of methyltrimethoxysilane and (N,N-dimethyl-3-aminopropyl)trimethoxysilane is a cage-type structure, which can effectively improve the mechanical properties of the fiber; the breaking strength of Examples 1 to 3 is significantly greater than that of Comparative Example 4, indicating that the tertiary amine on (N,N-dimethyl-3-aminopropyl)trimethoxysilane reacts with the polyester material to form a quaternary ammonium salt, so that the polysilsesquioxane forms a stable crosslink with the polyester fiber, thereby improving the mechanical properties of the fiber.

[0033] Test Example 4 Antibacterial performance test: Antibacterial performance: The antibacterial fibers obtained in each embodiment and comparative example were crushed, passed through a 100-mesh sieve, and the same mass was taken to test the antibacterial rate of the materials against Staphylococcus aureus according to the Quine test method. The results are shown in Table 4.

[0034] Table 4

[0035] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 3, it can be found that the antibacterial fiber prepared in the present invention has good antibacterial properties.

[0036] By comparison, the antibacterial rates of Examples 1 to 3 are greater than those of Comparative Examples 2 and 4, indicating that the tertiary amine on the (N, N-dimethyl-3-aminopropyl)trimethoxysilane on the polysilsesquioxane reacts with the polyester material to form a quaternary ammonium salt, which acts as a cationic antibacterial agent and improves the antibacterial properties of the biodegradable fiber.

[0037] Test Example 5 Hydrophilic performance test: Test method: The moisture regain test of the embodiment and the comparative example was carried out according to GB / T6503-2017 "Test method for moisture regain of chemical fibers". The results are shown in Table 5.

[0038] Table 5

[0039] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 5, it can be found that the biodegradable fiber prepared by the present invention has good hydrophilic properties.

[0040] By comparison, the moisture regains of Examples 1 to 3 are greater than those of Comparative Examples 2 and 4, indicating that the tertiary amine on polysilsesquioxane (N, N-dimethyl-3-aminopropyl)trimethoxysilane reacts with the polyester material to form a quaternary ammonium salt, which acts as a hydrophilic group and improves the hydrophilic properties of the biodegradable fiber.

[0041] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A biodegradable fiber, characterized in that: The biodegradable fiber is prepared by reacting modified vanillin, polysilsesquioxane and polyester material; The modified vanillin is prepared by reacting vanillin and N-aminomaleimide; The polysilsesquioxane is prepared by reacting methyltrimethoxysilane and (N,N-dimethyl-3-aminopropyl)trimethoxysilane; The polyester material is prepared by reacting adipic acid, 2,5-furandicarboxylic acid, (4-chlorophenyl)-diethyl phosphate and ethylene glycol.

2. A method for preparing biodegradable fiber, characterized in that: The method comprises the following preparation steps: (1) Vanillin, N-aminomaleimide and anhydrous ethanol are mixed in a mass ratio of 1: (1.3-1.7): (15-25), stirred at 400-600 r / min at 35-45°C for 3-5 h, and rotary evaporated at 40-50°C for 6-8 h to obtain modified vanillin; (2) Methyltrimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, methyl ethyl ketone and anhydrous methanol were mixed in a mass ratio of 1:(0.2~0.4):(18~22):(3~5), and a 0.1 mol / L sodium hydroxide aqueous solution (0.05~0.15 times the mass of methyl ethyl ketone) was added dropwise at a rate of 2~4 ml / min at 0°C. After the addition was completed, the reaction was continued for 0.5~1.5 h, and the temperature was raised to 70~80°C and the reaction was continued for 22~26 h. The organic phase was extracted and washed with dichloromethane for 3~5 times, and the organic phase was taken and distilled at 50~60°C under reduced pressure for 4~6 h to obtain polysilsesquioxane; (3) Adipic acid, 2,5-furandicarboxylic acid and ethylene glycol are added to a reactor in a molar ratio of 1:1:2, nitrogen is introduced, ethylene glycol antimony in an amount of 0.0003-0.0007 times the mass of 2,5-furandicarboxylic acid is added, stirring is carried out at 180-200°C and a speed of 200-400 r / min for 1-2 hours, (4-chlorobenzyl) dimethyl phosphate in an amount of 1-1.4 times the molar number of adipic acid is added, the temperature is raised to 195-205°C and the reaction is continued. When esterification water is no longer distilled, the pressure is adjusted to 90-110 Pa within 30 minutes, the temperature is raised to 230-240°C, the speed is adjusted to 50-70 r / min and stirring is carried out until the reaction is terminated, nitrogen is introduced to restore the pressure to normal pressure, the mixture is cooled to room temperature, and the polyester material is obtained by discharging; (4) The polyester material, polysilsesquioxane, modified vanillin, aluminum chloride and chloroform are mixed, stirred at 400-600 r / min at 55-65°C for 3-5 h, cooled to room temperature to obtain a spinning solution, and the fiber is prepared by electrospinning technology. The fiber is dried at 75-85°C for 4-6 h and cooled to room temperature to obtain a biodegradable fiber.

3. The method for preparing a biodegradable fiber according to claim 2, characterized in that: The reaction process of preparing modified vanillin in step (1) is as follows: .

4. The method for preparing a biodegradable fiber according to claim 2, characterized in that: The mass ratio of the polyester material, polysilsesquioxane, modified vanillin, aluminum chloride and chloroform in step (4) is 1: (0.2-0.4): (0.2-0.4): (0.04-0.06): (15-25).

5. The method for preparing a biodegradable fiber according to claim 2, characterized in that: The electrospinning process parameters of step (4) are: propulsion rate 0.6 ml / h, voltage 23 kV, receiving distance 12 cm, and ambient humidity 40-50%.

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