Anti-aging biodegradable material and preparation method thereof

Abstract

The invention discloses an anti-aging biodegradable material and a preparation method thereof, and relates to the technical field of high polymer materials. When the anti-aging biodegradable material is prepared, rutin and ethyl chlorophosphate epoxypropyl ester react to prepare modified rutin; the preparation method comprises the following steps: polymerizing ionone dimethyl glutarate, alpha-hydroxyl-omega-carboxyl oligomeric lactic acid, 1, 6-hexanediol and 3-(1H-imidazole-1-yl) propane-1, 2-diol to obtain oligomeric lactic acid copolyester; the straw powder and 4-(1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxan-3-yl) butyl chloride are subjected to a reaction, and modified straw powder is prepared; and uniformly mixing the oligomeric lactic acid copolyester, the modified straw powder and the modified rutin, and performing injection molding in an injection molding machine to obtain the anti-aging biodegradable material. The anti-aging biodegradable material prepared by the invention has excellent anti-aging, flame-retardant and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to an anti-aging biodegradable material and a preparation method thereof. Background Art

[0002] Biodegradable materials are materials that, under appropriate natural conditions, can be completely decomposed by microorganisms (such as bacteria, fungi, and algae) into low-molecular compounds (such as water and carbon dioxide). They are used in a wide range of fields, including packaging, agriculture, healthcare, and textiles, producing products such as food packaging, express packaging, agricultural mulch, seedling pots, and surgical sutures. The use of biodegradable materials can alleviate white pollution and protect the ecological environment. Traditional plastics (such as polyethylene and polypropylene) take hundreds of years to degrade in the natural environment, while biodegradable materials (such as PLA and PHA) can be broken down by microorganisms into water, carbon dioxide, and organic matter, significantly reducing soil and marine pollution. Microplastics produced by the decomposition of traditional plastics can enter the food chain, posing a threat to organisms and human health. Biodegradable materials can also alleviate waste disposal pressures. Compostable materials can reduce the burden on landfills and reduce harmful gas emissions from incineration.

[0003] While biodegradable materials produced using existing technologies exhibit good degradation properties, their performance (such as mechanical properties and aging resistance) is generally inferior to that of traditional petrochemical materials, making them difficult to meet application requirements. This is particularly true when used as agricultural mulch, where prolonged exposure to sunlight often leads to performance degradation. Therefore, there is a need to develop biodegradable materials with superior aging resistance that simultaneously meet both application and environmental requirements. Summary of the Invention

[0004] The purpose of the present invention is to provide an anti-aging biodegradable material 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: An anti-aging biodegradable material is prepared by polymerizing ionone dimethyl glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol to obtain oligolactic acid copolyester; uniformly mixing the oligolactic acid copolyester, modified straw powder, and modified rutin, and performing injection molding in an injection molding machine to obtain the anti-aging biodegradable material. The ionone dimethyl glutarate is prepared by reacting 3-acyl chloride-1,5-dimethyl glutarate and 3-hydroxy-β-ionone; The α-hydroxy-ω-carboxyl oligomeric lactic acid is prepared by self-polymerization of DL-lactic acid; The modified rutin is prepared by reacting rutin with ethyl chlorophosphate glycidyl ester; The modified straw powder is prepared by reacting straw powder and 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride.

[0006] A method for preparing an anti-aging biodegradable material, comprising the following steps: (1) Weigh rutin and ethyl chlorophosphate glycidyl ester in a molar ratio of 1:3; prepare a modification solution by adding ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol; mix rutin and anhydrous ethanol in a mass ratio of 1:(14-16) evenly, add the modification solution dropwise at a constant speed within 30 minutes at room temperature under stirring conditions of 200-300 r / min, continue stirring and reacting at room temperature for 16-18 hours after the addition is completed, and dry at 50-60°C under vacuum conditions for 8-10 hours to obtain modified rutin; (2) Mix dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazole-1-yl)propane-1,2-diol in a molar ratio of 1:(0.7~0.8):(0.7~0.8):(0.5~0.6) evenly, add tetrabutyl titanate (0.04~0.06 times the mass of dimethyl ionone glutarate), and stir at 200℃ and 80~100r / min for 2h under nitrogen protection. Reduce the pressure of the reaction system to below 50Pa, raise the temperature to 260℃ and continue stirring for 2h to obtain oligolactic acid copolyester; (3) Mix straw powder and dimethyl sulfoxide in a mass ratio of 1:(5-6), stir at 40-50°C and 200-300 r / min for 20-30 min, add 4-dimethylaminopyridine (0.1-0.12 times the mass of straw powder) and triethylamine (0.05-0.07 times the mass of straw powder), continue stirring for 4-6 min, add the reaction solution (10-12 times the mass of straw powder) at a uniform speed within 20 min, continue stirring and reacting for 4-6 h after the addition is complete, cool to room temperature, filter, wash with anhydrous ethanol 4-6 times, and dry at 50-60°C under vacuum conditions for 8-10 h to obtain modified straw powder; (4) Oligomeric lactic acid copolyester, modified straw powder and modified rutin were mixed evenly in a mass ratio of 1:(0.06~0.07):(0.09~0.1), placed in an injection molding machine for injection molding, and kept at 100℃ for 3h after injection molding, then heated to 140℃ and kept for 3h, and naturally cooled to room temperature to obtain an anti-aging biodegradable material.

[0007] As an optimization, the preparation method of the modified liquid in step (1) is as follows: ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol are uniformly mixed in a mass ratio of 1: (0.03~0.05): (8~10) to prepare a modified liquid.

[0008] As an optimization, the CAS number of the ethyl chlorophosphate glycidyl ester in step (1) is 209793-69-1; the structural formula is: .

[0009] As an optimization, the preparation method of ionone dimethyl glutarate in step (2) is as follows: 3-acyl chloride-1,5-dimethyl glutarate and 3-hydroxy-β-ionone are added in a molar ratio of 1:1 to tetrahydrofuran with a mass of 15 to 17 times that of 3-acyl chloride-1,5-dimethyl glutarate, and triethylamine with a mass of 0.05 to 0.06 times that of 3-acyl chloride-1,5-dimethyl glutarate is added, and the mixture is stirred at 50 to 60°C and 300 to 400 r / min for 8 to 10 hours, and dried at 50 to 60°C under vacuum conditions for 10 to 12 hours to obtain ionone dimethyl glutarate.

[0010] As an optimization, the CAS number of the dimethyl 3-acyl chloride-1,5-pentanedioate is 61495-23-6; the structural formula is: .

[0011] As an optimization, the preparation method of the α-hydroxy-ω-carboxyl oligomeric lactic acid in step (2) is as follows: DL-lactic acid and deionized water are uniformly mixed to prepare a lactic acid aqueous solution with a mass fraction of 90%; the lactic acid aqueous solution is stirred at 100°C and 80-100 r / min for 1 hour, the temperature is raised to 200°C, the stirring reaction is continued for 2 hours, the pressure of the reaction system is reduced to 0.7-0.9 kPa, and the temperature is kept at 200°C for 4 hours to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid.

[0012] As an optimization, the preparation method of the reaction solution in step (3) is as follows: 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride and dimethyl sulfoxide are uniformly mixed in a mass ratio of 1:(6~7) to prepare a reaction solution.

[0013] As an optimization, the CAS number of the 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride is 63672-07-1; the structural formula is: .

[0014] As an optimization, the particle size of the straw powder in step (3) is 800 mesh.

[0015] As an optimization, the process parameters of the injection molding in step (4) are as follows: the barrel temperature of the injection molding machine is 160~165℃, the mold temperature is 60~70℃, the injection pressure is 70MPa, the screw speed is 60r / min, the holding pressure is 30MPa, and the holding time is 8~10s.

[0016] Compared with the prior art, the present invention has the following beneficial effects: When preparing the anti-aging biodegradable material, the present invention comprises the following steps: reacting rutin with ethyl chlorophosphate glycidyl to obtain modified rutin; reacting 3-acyl chloride-1,5-dimethyl glutarate and 3-hydroxy-β-ionone to obtain iononyl glutarate dimethyl ester; self-polymerizing DL-lactic acid to obtain α-hydroxy-ω-carboxyl oligolactic acid; polymerizing iononyl glutarate dimethyl ester, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol and 3-(1H-imidazole-1-yl)propane-1,2-diol to obtain oligolactic acid copolyester; reacting straw powder and 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride to obtain modified straw powder; and uniformly mixing the oligolactic acid copolyester, the mixture and the mixture are placed in an injection molding machine for injection molding to obtain the anti-aging biodegradable material.

[0017] First, some hydroxyl groups on rutin are reacted with the P-Cl bonds on ethyl chlorophosphate glycidyl ester to produce modified rutin, and phosphorus and epoxy groups are introduced into the modified rutin. Rutin is a flavonoid compound that exists in large quantities in plants in nature. Rutin has a conjugated structure and can absorb ultraviolet radiation. When ultraviolet rays irradiate rutin, its molecules are excited from the ground state to the excited state (higher energy state). The excited molecules return to the ground state through emission wave radiation, thereby improving the anti-aging properties of the anti-aging biodegradable material. The phosphorus element introduced into the modified rutin can improve the flame retardant properties of the anti-aging biodegradable material. The epoxy group introduced into the modified rutin can react with the imidazole group introduced into the side chain of the oligolactic acid copolyester molecule, and a cross-linked network structure is formed through programmed temperature curing, thereby improving the mechanical properties of the anti-aging biodegradable material.

[0018] Secondly, the acyl chloride group on 3-acyl chloride-1,5-pentanedioic acid dimethyl ester reacts with the hydroxyl group on 3-hydroxy-β-ionone to prepare ionone dimethyl glutarate; DL-lactic acid is self-polymerized to prepare α-hydroxy-ω-carboxyl oligolactic acid; ionone dimethyl glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol are polymerized to prepare oligolactic acid copolyester; β-ionone structure and imidazole group are introduced into the side chain of the oligolactic acid copolyester molecule; the β-ionone structure can undergo cis-trans isomerization under the action of ultraviolet light, changing from Z configuration to E configuration, and this configuration change is reversible. By utilizing this property, ultraviolet light energy is converted into chemical energy, thereby further improving the anti-aging performance of the anti-aging biodegradable material. The mechanism of action is shown in the following formula: ; The imidazole groups introduced on the side chains of oligolactic acid copolyester molecules serve as cross-linking sites, and are cured through programmed temperature increase with the epoxy groups introduced on the modified rutin to form a cross-linking network, thereby improving the mechanical properties of the anti-aging biodegradable material.

[0019] Finally, the hydroxyl groups on the straw powder reacted with the acyl chloride groups on 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride to produce modified straw powder, and siloxane chains were introduced into the modified straw powder; the introduction of siloxane chains can further improve the flame retardant properties; straw powder is widely available and has a huge annual output, but the molecular structure of straw powder contains a large number of hydrophilic hydroxyl groups, which makes it difficult to process and has poor compatibility with resin materials. Directly adding straw powder to the resin will result in uneven dispersion, resulting in reduced overall performance of the composite material; using 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride to modify the surface of straw powder can reduce the hydrophilicity of the straw powder and improve its interfacial compatibility with the resin matrix.

[0020] The present invention uses a variety of biomass raw materials when preparing the anti-aging biodegradable material, reducing the use of petrochemical raw materials. At the same time, the obtained material is easily degraded in the natural environment, which is of great significance to protecting the environment and saving resources. DETAILED DESCRIPTION

[0021] 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 embodiments described 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 efforts are within the scope of protection of the present invention.

[0022] Example 1: A method for preparing an anti-aging biodegradable material, comprising the following steps: (1) Weigh rutin and ethyl chlorophosphate glycidyl ester in a molar ratio of 1:3; mix ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol in a mass ratio of 1:0.03:8 to prepare a modified solution; mix rutin and anhydrous ethanol in a mass ratio of 1:14, add the modified solution dropwise at a constant speed within 30 minutes at room temperature and stirring at 200 r / min, continue stirring at room temperature for 18 hours after the addition is completed, and dry at 50°C for 10 hours under vacuum conditions to obtain modified rutin; (2) Add 3-acyl chloride-1,5-pentanedioic acid dimethyl ester and 3-hydroxy-β-ionone in a molar ratio of 1:1 to tetrahydrofuran (15 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), add triethylamine (0.05 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), stir and react at 50℃, 300r / min for 10h, and dry at 50℃ for 12h under vacuum conditions to obtain ionone glutaric acid dimethyl ester; mix DL-lactic acid and deionized water evenly to prepare a lactic acid aqueous solution with a mass fraction of 90%; stir and react the lactic acid aqueous solution at 100℃, 80r / min for 1h, heat to 200℃, and continue stirring. The mixture was stirred and reacted for 2 hours, the pressure of the reaction system was reduced to 0.7 kPa, and the mixture was kept at 200° C. for 4 hours to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid; dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligomeric lactic acid, 1,6-hexanediol, and 3-(1H-imidazole-1-yl)propane-1,2-diol were mixed uniformly in a molar ratio of 1:0.7:0.7:0.5, and tetrabutyl titanate (0.04 times the mass of dimethyl ionone glutarate) was added. Under nitrogen protection, the mixture was stirred and reacted at 200° C. and 80 r / min for 2 hours, the pressure of the reaction system was reduced to below 50 Pa, the temperature was raised to 260° C., and the stirring reaction was continued for 2 hours to obtain oligomeric lactic acid copolyester; (3) 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride and dimethyl sulfoxide were mixed at a mass ratio of 1:6 to prepare a reaction solution; straw powder and dimethyl sulfoxide were mixed at a mass ratio of 1:5, stirred at 40°C and 200 r / min for 30 min, 4-dimethylaminopyridine (0.1 times the mass of the straw powder) and triethylamine (0.05 times the mass of the straw powder) were added, and the stirring was continued for 6 min. The reaction solution (10 times the mass of the straw powder) was added dropwise at a uniform speed within 20 min. After the addition was completed, the reaction was continued with stirring for 6 h, cooled to room temperature, filtered, washed with anhydrous ethanol 4 times, and dried at 50°C under vacuum conditions for 10 h to obtain modified straw powder; (4) The oligomeric lactic acid copolyester, modified straw powder and modified rutin were mixed evenly in a mass ratio of 1:0.06:0.09 and placed in an injection molding machine for injection molding. The barrel temperature of the injection molding machine was 160°C, the mold temperature was 60°C, the injection pressure was 70 MPa, the screw speed was 60 r / min, the holding pressure was 30 MPa, and the holding time was 10 s. After injection molding, the mixture was kept at 100°C for 3 h, then heated to 140°C for 3 h, and naturally cooled to room temperature to obtain an anti-aging biodegradable material.

[0023] Example 2: A method for preparing an anti-aging biodegradable material, comprising the following steps: (1) Weigh rutin and ethyl chlorophosphate glycidyl ester in a molar ratio of 1:3; mix ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol in a mass ratio of 1:0.04:9 to prepare a modified solution; mix rutin and anhydrous ethanol in a mass ratio of 1:15, add the modified solution dropwise at a constant speed within 30 minutes at room temperature and stirring at 250 r / min, continue stirring at room temperature for 17 hours after the addition is completed, and dry at 55°C under vacuum for 9 hours to obtain modified rutin; (2) Add 3-acyl chloride-1,5-pentanedioic acid dimethyl ester and 3-hydroxy-β-ionone in a molar ratio of 1:1 to tetrahydrofuran (16 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), add triethylamine (0.055 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), stir and react at 55°C, 350r / min for 9h, and dry at 55°C under vacuum for 11h to obtain ionone glutaric acid dimethyl ester; mix DL-lactic acid and deionized water evenly to prepare a lactic acid aqueous solution with a mass fraction of 90%; stir and react the lactic acid aqueous solution at 100°C, 90r / min for 1h, heat to 200°C, and continue stirring to react; The reaction mixture was stirred for 2 h, the pressure of the reaction system was reduced to 0.8 kPa, and the mixture was kept at 200 ° C for 4 h to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid; dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligomeric lactic acid, 1,6-hexanediol, and 3-(1H-imidazole-1-yl)propane-1,2-diol were mixed uniformly in a molar ratio of 1:0.75:0.75:0.55, and tetrabutyl titanate (0.05 times the mass of dimethyl ionone glutarate) was added. Under nitrogen protection, the mixture was stirred at 200 ° C and 90 r / min for 2 h, the pressure of the reaction system was reduced to below 50 Pa, the temperature was raised to 260 ° C and the stirring reaction was continued for 2 h to obtain oligomeric lactic acid copolyester; (3) 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride and dimethyl sulfoxide were mixed at a mass ratio of 1:6.5 to prepare a reaction solution; straw powder and dimethyl sulfoxide were mixed at a mass ratio of 1:5.5 to prepare a reaction solution; the mixture was stirred at 45°C and 250 r / min for 25 min, 4-dimethylaminopyridine (0.11 times the mass of the straw powder) and triethylamine (0.06 times the mass of the straw powder) were added, and the mixture was stirred for 5 min. The reaction solution (11 times the mass of the straw powder) was added dropwise at a constant speed within 20 min. After the addition was completed, the mixture was stirred for 5 h, cooled to room temperature, filtered, washed with anhydrous ethanol 5 times, and dried at 55°C under vacuum for 9 h to obtain modified straw powder; (4) The oligomeric lactic acid copolyester, modified straw powder and modified rutin were mixed evenly in a mass ratio of 1:0.065:0.095 and placed in an injection molding machine for injection molding. The barrel temperature of the injection molding machine was 162.5°C, the mold temperature was 65°C, the injection pressure was 70 MPa, the screw speed was 60 r / min, the holding pressure was 30 MPa, and the holding time was 9 s. After injection molding, the mixture was kept at 100°C for 3 h, then heated to 140°C for 3 h, and naturally cooled to room temperature to obtain an anti-aging biodegradable material.

[0024] Example 3: A method for preparing an anti-aging biodegradable material, comprising the following steps: (1) Weigh rutin and ethyl chlorophosphate glycidyl ester in a molar ratio of 1:3; mix ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol in a mass ratio of 1:0.05:10 to prepare a modified solution; mix rutin and anhydrous ethanol in a mass ratio of 1:16, add the modified solution dropwise at a constant speed within 30 minutes at room temperature and stirring at 300 r / min, continue stirring at room temperature for 16 hours after the addition is completed, and dry at 60°C under vacuum for 8 hours to obtain modified rutin; (2) Add 3-acyl chloride-1,5-pentanedioic acid dimethyl ester and 3-hydroxy-β-ionone in a molar ratio of 1:1 to tetrahydrofuran (17 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), add triethylamine (0.06 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), stir and react at 60°C, 400 r / min for 8 hours, and dry at 60°C under vacuum for 10 hours to obtain ionone glutaric acid dimethyl ester; mix DL-lactic acid and deionized water evenly to prepare a lactic acid aqueous solution with a mass fraction of 90%; stir and react the lactic acid aqueous solution at 100°C, 100 r / min for 1 hour, heat to 200°C, and continue stirring. The reaction was continued for 2 hours, the pressure of the reaction system was reduced to 0.9 kPa, and the mixture was kept at 200°C for 4 hours to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid; dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligomeric lactic acid, 1,6-hexanediol, and 3-(1H-imidazole-1-yl)propane-1,2-diol were mixed uniformly in a molar ratio of 1:0.8:0.8:0.6, and tetrabutyl titanate (0.06 times the mass of dimethyl ionone glutarate) was added. Under nitrogen protection, the mixture was stirred at 200°C and 100 r / min for 2 hours, the pressure of the reaction system was reduced to below 50 Pa, the temperature was raised to 260°C, and the stirring reaction was continued for 2 hours to obtain oligomeric lactic acid copolyester; (3) 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride and dimethyl sulfoxide were mixed at a mass ratio of 1:7 to prepare a reaction solution; straw powder and dimethyl sulfoxide were mixed at a mass ratio of 1:6, stirred at 50°C and 300 r / min for 20 min, 4-dimethylaminopyridine (0.12 times the mass of straw powder) and triethylamine (0.07 times the mass of straw powder) were added, and the stirring was continued for 4 min. The reaction solution (12 times the mass of straw powder) was added dropwise at a uniform speed within 20 min. After the addition was completed, the reaction was continued with stirring for 4 h, cooled to room temperature, filtered, washed with anhydrous ethanol 6 times, and dried at 60°C under vacuum conditions for 8 h to obtain modified straw powder; (4) The oligomeric lactic acid copolyester, modified straw powder and modified rutin were mixed evenly in a mass ratio of 1:0.07:0.1 and placed in an injection molding machine for injection molding. The barrel temperature of the injection molding machine was 165°C, the mold temperature was 70°C, the injection pressure was 70 MPa, the screw speed was 60 r / min, the holding pressure was 30 MPa, and the holding time was 8 s. After injection molding, the mixture was kept at 100°C for 3 h, then heated to 140°C for 3 h, and naturally cooled to room temperature to obtain an anti-aging biodegradable material.

[0025] Comparative Example 1: The preparation method of the anti-aging biodegradable material of Comparative Example 1 differs from that of Example 2 in that step (1) is omitted and step (4) is modified as follows: oligolactic acid copolyester, modified straw powder, and rutin are uniformly mixed in a mass ratio of 1:0.065:0.095, and the mixture is placed in an injection molding machine for injection molding. The injection molding machine barrel temperature is 162.5°C, the mold temperature is 65°C, the injection pressure is 70 MPa, the screw speed is 60 r / min, the holding pressure is 30 MPa, and the holding time is 9 s. After injection molding, the mixture is kept at 100°C for 3 h, then heated to 140°C for 3 h, and then naturally cooled to room temperature to obtain the anti-aging biodegradable material. The remaining steps are the same as those of Example 2.

[0026] Comparative Example 2: The preparation method of the anti-aging biodegradable material of Comparative Example 2 differs from that of Example 2 in that step (1) is omitted and step (4) is modified as follows: oligolactic acid copolyester and modified straw powder are uniformly mixed in a mass ratio of 1:0.065, and the mixture is placed in an injection molding machine for injection molding. The injection molding machine barrel temperature is 162.5°C, the mold temperature is 65°C, the injection pressure is 70 MPa, the screw speed is 60 r / min, the holding pressure is 30 MPa, and the holding time is 9 s. After injection molding, the mixture is kept at 100°C for 3 h, then heated to 140°C for 3 h, and then naturally cooled to room temperature to obtain the anti-aging biodegradable material. The remaining steps are the same as those of Example 2.

[0027] Comparative Example 3: The preparation method of the anti-aging biodegradable material of Comparative Example 3 differs from that of Example 2 only in step (2). Step (2) is modified as follows: DL-lactic acid and deionized water are uniformly mixed to prepare a lactic acid aqueous solution with a mass fraction of 90%; the lactic acid aqueous solution is stirred and reacted at 100°C and 90 r / min for 1 hour, the temperature is raised to 200°C, the stirring reaction is continued for 2 hours, the pressure of the reaction system is reduced to 0.8 kPa, and the temperature is kept at 200°C for 4 hours to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid; Dimethyl glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol were uniformly mixed in a molar ratio of 1:0.75:0.75:0.55. Tetrabutyl titanate (0.05 times the mass of dimethyl glutarate) was added. Under nitrogen protection, the mixture was stirred at 200°C and 90 rpm for 2 hours. The pressure of the reaction system was reduced to below 50 Pa, and the temperature was raised to 260°C, where stirring was continued for 2 hours to produce an oligolactic acid copolyester. The remaining steps were the same as in Example 2.

[0028] Comparative Example 4: The preparation method of the anti-aging biodegradable material of Comparative Example 4 differs from that of Example 2 only in step (2). Step (2) is modified as follows: 3-acyl chloride-1,5-pentanedioic acid dimethyl ester and 3-hydroxy-β-ionone are added in a molar ratio of 1:1 to tetrahydrofuran (16 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester), triethylamine (0.055 times the mass of 3-acyl chloride-1,5-pentanedioic acid dimethyl ester) is added, the mixture is stirred at 55°C and 350 r / min for 9 hours, and dried at 55°C under vacuum conditions for 11 hours to obtain ionone-based glutaric acid dimethyl ester; DL-lactic acid is evenly mixed with deionized water to prepare a lactic acid aqueous solution with a mass fraction of 90%; the lactic acid aqueous solution is added The reaction was stirred at 100°C and 90 rpm for 1 hour, then heated to 200°C and stirred for 2 hours. The pressure of the reaction system was reduced to 0.8 kPa, and the reaction was kept at 200°C for 4 hours to produce α-hydroxy-ω-carboxyl oligomeric lactic acid. Ionone dimethyl glutarate, α-hydroxy-ω-carboxyl oligomeric lactic acid, 1,6-hexanediol, and ethylene glycol were uniformly mixed in a molar ratio of 1:0.75:0.75:0.55, and tetrabutyl titanate (0.05 times the mass of ionone dimethyl glutarate) was added. Under nitrogen protection, the reaction was stirred at 200°C and 90 rpm for 2 hours. The pressure of the reaction system was reduced to below 50 Pa, and the reaction was continued by heating to 260°C and stirring for 2 hours to produce oligomeric lactic acid copolyester. The remaining steps were the same as in Example 2.

[0029] Comparative Example 5: The preparation method of the anti-aging biodegradable material of Comparative Example 5 differs from that of Example 2 in that step (3) is omitted and step (4) is modified as follows: oligolactic acid copolyester, straw powder, and modified rutin are uniformly mixed in a mass ratio of 1:0.065:0.095, and the mixture is placed in an injection molding machine for injection molding. The injection molding machine barrel temperature is 162.5°C, the mold temperature is 65°C, the injection pressure is 70 MPa, the screw speed is 60 r / min, the holding pressure is 30 MPa, and the holding time is 9 s. After injection molding, the mixture is kept at 100°C for 3 h, then heated to 140°C for 3 h, and then naturally cooled to room temperature to obtain the anti-aging biodegradable material. The remaining steps are the same as those of Example 2.

[0030] Test Example 1 Testing of mechanical properties and anti-aging properties Testing Method: According to GB / T 1040, Type I standard bars from the examples and comparative examples were prepared. Their tensile strength (M1) was measured using an electronic universal testing machine. The standard bars were then placed in an aging chamber and irradiated with 200W, 365nm UV light for 10 days. Their tensile strength (M2) was then measured. The performance degradation rates of the examples and comparative examples before and after the UV aging test were calculated as (M1 - M2) / M1 × 100%. The results are shown in Table 1.

[0031] Table 1

[0032] 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 anti-aging biodegradable material prepared by the present invention has good mechanical properties and anti-aging properties.

[0033] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Examples 1 to 2, indicating that some hydroxyl groups on rutin react with the P-Cl bonds on ethyl chlorophosphate glycidyl ester to prepare modified rutin, and epoxy groups are introduced into the modified rutin; the epoxy groups introduced into the modified rutin can react with the imidazole groups introduced into the side chains of the oligolactic acid copolyester molecules, forming a cross-linked network structure through programmed temperature curing, thereby improving the mechanical properties of the anti-aging biodegradable material.

[0034] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol are polymerized to prepare oligolactic acid copolyesters; imidazole groups are introduced into the side chains of the oligolactic acid copolyester molecules; the imidazole groups introduced into the side chains of the oligolactic acid copolyester molecules serve as cross-linking sites, and are cured through programmed temperature rise with the epoxy groups introduced into the modified rutin to form a cross-linked network, thereby improving the mechanical properties of the anti-aging biodegradable material.

[0035] By comparison, the performance degradation rates of Examples 1 to 3 are less than that of Comparative Example 2, indicating that the addition of rutin can improve the anti-aging performance of the material. This is because rutin is a flavonoid compound that exists in large quantities in plants in nature. Rutin has a conjugated structure and can absorb ultraviolet radiation.

[0036] By comparison, the performance degradation rates of Examples 1 to 3 are less than that of Comparative Example 3, indicating that the acyl chloride group on 3-acylchloride-1,5-dimethyl glutarate reacts with the hydroxyl group on 3-hydroxy-β-ionone to prepare iononyl glutarate dimethyl ester; DL-lactic acid is self-polymerized to prepare α-hydroxy-ω-carboxyl oligolactic acid; iononyl glutarate dimethyl ester, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol are polymerized to prepare oligomeric lactic acid copolyester; a β-ionone structure is introduced into the side chain of the oligomeric lactic acid copolyester molecule; the β-ionone structure can undergo cis-trans isomerization under the action of ultraviolet light, changing from a Z configuration to an E configuration, and this configuration change is reversible. By utilizing this property, ultraviolet light energy is converted into chemical energy, thereby further improving the anti-aging performance of the anti-aging biodegradable material.

[0037] Test Example 2 Flame retardant performance test Test method: The limiting oxygen index values ​​of the examples and comparative examples were tested according to ISO 4589-2 standard. The test sample size was 100×10×0.4 mm. The results are shown in Table 2.

[0038] Table 2

[0039] 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 anti-aging biodegradable material prepared by the present invention has good flame retardant properties.

[0040] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Examples 1 to 2, indicating that some hydroxyl groups on rutin react with the P-Cl bond on ethyl chlorophosphate glycidyl ester to prepare modified rutin, and phosphorus is introduced into the modified rutin; the phosphorus introduced into the modified rutin can improve the flame retardant properties of the anti-aging biodegradable material.

[0041] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 5, indicating that the hydroxyl groups on the straw powder react with the acyl chloride groups on 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride to produce modified straw powder, and siloxane chains are introduced into the modified straw powder; the introduction of siloxane chains can further improve the flame retardant properties.

[0042] 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. An anti-aging biodegradable material, characterized in that: The anti-aging biodegradable material is prepared by polymerizing ionone dimethyl glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazol-1-yl)propane-1,2-diol to obtain oligolactic acid copolyester; and uniformly mixing the oligolactic acid copolyester, modified straw powder, and modified rutin, and performing injection molding in an injection molding machine. The ionone dimethyl glutarate is prepared by reacting 3-acyl chloride-1,5-dimethyl glutarate and 3-hydroxy-β-ionone; The α-hydroxy-ω-carboxyl oligomeric lactic acid is prepared by self-polymerization of DL-lactic acid; The modified rutin is prepared by reacting rutin with ethyl chlorophosphate glycidyl ester; The modified straw powder is prepared by reacting straw powder and 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride.

2. A method for preparing an anti-aging biodegradable material, characterized in that: The preparation method of the anti-aging biodegradable material comprises the following preparation steps: (1) Weigh rutin and ethyl chlorophosphate glycidyl ester in a molar ratio of 1:3; prepare a modification solution by adding ethyl chlorophosphate glycidyl ester, triethylamine, and anhydrous ethanol; mix rutin and anhydrous ethanol in a mass ratio of 1:(14-16) evenly, add the modification solution dropwise at a constant speed within 30 minutes at room temperature under stirring conditions of 200-300 r / min, continue stirring and reacting at room temperature for 16-18 hours after the addition is completed, and vacuum dry to obtain modified rutin; (2) Mix dimethyl ionone glutarate, α-hydroxy-ω-carboxyl oligolactic acid, 1,6-hexanediol, and 3-(1H-imidazole-1-yl)propane-1,2-diol in a molar ratio of 1:(0.7~0.8):(0.7~0.8):(0.5~0.6) evenly, add tetrabutyl titanate (0.04~0.06 times the mass of dimethyl ionone glutarate), react at 200℃ for 2h under nitrogen protection, reduce the pressure of the reaction system to below 50Pa, heat to 260℃ and continue to react for 2h to obtain oligolactic acid copolyester; (3) Mix straw powder and dimethyl sulfoxide in a mass ratio of 1:(5-6), stir at 40-50 °C for 20-30 min, add 4-dimethylaminopyridine (0.1-0.12 times the mass of straw powder) and triethylamine (0.05-0.07 times the mass of straw powder), continue stirring for 4-6 min, and add the reaction solution (10-12 times the mass of straw powder) at a uniform speed within 20 min. After the addition is complete, continue stirring and reacting for 4-6 h, cool to room temperature, filter, wash, and vacuum dry to obtain modified straw powder; (4) Oligomeric lactic acid copolyester, modified straw powder and modified rutin were mixed evenly in a mass ratio of 1:(0.06~0.07):(0.09~0.1), placed in an injection molding machine for injection molding, and kept at 100℃ for 3h after injection molding, then heated to 140℃ and kept for 3h, and naturally cooled to room temperature to obtain an anti-aging biodegradable material.

3. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The preparation method of the modified liquid in step (1) is as follows: ethyl chlorophosphate, glycidyl ester, triethylamine, and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(0.03-0.05):(8-10) to prepare a modified liquid.

4. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The preparation method of ionone dimethyl glutarate in step (2) is as follows: 3-acyl chloride-1,5-dimethyl glutarate and 3-hydroxy-β-ionone are added in a molar ratio of 1:1 to tetrahydrofuran with a mass of 15 to 17 times that of 3-acyl chloride-1,5-dimethyl glutarate, and triethylamine with a mass of 0.05 to 0.06 times that of 3-acyl chloride-1,5-dimethyl glutarate is added, the mixture is reacted at 50 to 60° C. for 8 to 10 hours, and vacuum dried to obtain ionone dimethyl glutarate.

5. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The preparation method of the α-hydroxy-ω-carboxyl oligomeric lactic acid in step (2) is as follows: DL-lactic acid and deionized water are uniformly mixed to prepare a lactic acid aqueous solution with a mass fraction of 90%; the lactic acid aqueous solution is reacted at 100° C. for 1 hour, the temperature is raised to 200° C. and the reaction is continued for 2 hours, the pressure of the reaction system is reduced to 0.7~0.9 kPa, and the temperature is kept at 200° C. for 4 hours to obtain α-hydroxy-ω-carboxyl oligomeric lactic acid.

6. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The preparation method of the reaction solution in step (3) is as follows: 4-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)butyl chloride and dimethyl sulfoxide are uniformly mixed in a mass ratio of 1:(6~7) to prepare a reaction solution.

7. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The particle size of the straw powder in step (3) is 800 mesh.

8. The method for preparing an anti-aging biodegradable material according to claim 2, characterized in that: The process parameters of the injection molding in step (4) are as follows: the barrel temperature of the injection molding machine is 160-165°C, the mold temperature is 60-70°C, the injection pressure is 70 MPa, the screw speed is 60 r / min, the holding pressure is 30 MPa, and the holding time is 8-10 s.

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