Bone glue-based high-strength membrane material as well as preparation method and application thereof

Abstract

The invention discloses a bone glue-based high-strength membrane material which comprises the following raw materials in parts by mass: 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of a dispersion medium. The invention also discloses a preparation method of the bone glue-based high-strength membrane material, which comprises the following steps: by taking glycerol and maleic anhydride as raw materials, carrying out esterification reaction to synthesize hydroxyl-terminated hyperbranched polyester; and then compounding the composite material with bone glue through a solution blending-casting film forming process. Multiple hydrogen-bond interaction is formed between the hydroxyl-terminated hyperbranched polyester and bone glue molecules, so that the strength of the membrane material is improved; meanwhile, a large amount of free volume is generated among molecular chains due to the highly branched three-dimensional spherical structure, and the toughness of the material is effectively improved, so that the problem that a traditional small-molecule plasticizer is easy to migrate is solved. According to the prepared membrane material, biomass materials serve as main raw materials, certain biodegradability is achieved in the natural environment, the tensile strength is larger than or equal to 20 MPa, and the elongation at break is larger than or equal to 5%.

Description

Technical Field

[0001] This invention belongs to the field of biomass polymer material preparation technology, specifically relating to bone glue-based high-strength membrane materials, and also to the preparation method and application of such bone glue-based high-strength membrane materials. Background Technology

[0002] Bone glue, a natural protein-based biomass material, is mainly derived from animal bones, tendons, and other byproducts. It possesses good biocompatibility, biodegradability, and film-forming properties, making it potentially valuable in packaging, adhesives, and biomedicine. However, pure bone glue membranes suffer from high brittleness and poor flexibility due to strong intermolecular hydrogen bonding and hydrophobic interactions. To improve flexibility, small-molecule plasticizers such as glycerol and ethylene glycol are typically added. However, during use, these plasticizers easily migrate from the membrane to the surface, causing secondary brittleness and surface contamination, and significantly reducing the tensile strength of the membrane, severely limiting the practical application of bone glue membranes.

[0003] Hyperbranched polymers, as a class of polymeric materials with unique three-dimensional topological structures, are characterized by high end-group density, low molecular chain entanglement, and good solubility. Among them, hydroxyl-terminated hyperbranched polyesters contain a large number of terminal hydroxyl groups. When introduced into protein matrices, these hydroxyl groups can form multiple hydrogen bonds with amino and carboxyl groups in the matrix, increasing the crosslinking density of the material. At the same time, the highly branched structure can introduce more free volume into the matrix, effectively alleviating intermolecular aggregation and significantly improving the toughness of the material.

[0004] Based on the above background, a high-strength bone glue-based membrane material with bone glue as the base material and terminal hydroxyl hyperbranched polyester as the modifier is designed to solve the problems of high brittleness and easy migration of plasticizers in traditional bone glue membranes. This has important theoretical significance and practical application value. Summary of the Invention

[0005] The primary objective of this invention is to provide a high-strength bone glue-based membrane material, thereby addressing the problems of high brittleness and low strength in existing bone glue membrane materials.

[0006] A second objective of this invention is to provide a method for preparing a high-strength membrane material based on bone glue.

[0007] A third objective of this invention is to provide the application of bone glue-based high-strength film materials in agricultural films and packaging materials.

[0008] The technical solution adopted in this invention is a bone glue-based high-strength membrane material, comprising the following raw materials in parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium; wherein the dispersion medium is distilled water or deionized water; and wherein the hydroxyl-terminated hyperbranched polyester is synthesized by esterification reaction of glycerol and maleic anhydride.

[0009] The synthesis steps of hydroxyl-terminated hyperbranched polyester are as follows:

[0010] Glycerol and maleic anhydride in a molar ratio of 1:0.8-1.2 were mixed and reacted under nitrogen atmosphere at 70-80 °C for 1-2 h with stirring. Then, the mixture was reacted sequentially at 90-100 °C for 2 h, 110-120 °C for 2 h, and 130-140 °C for 3-5 h. After the reaction was completed, nitrogen was continued to be introduced and the mixture was allowed to cool naturally to 60-80 °C with stirring. A neutralizing agent was then added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the mixture was distilled under reduced pressure at -0.08 MPa to -0.095 MPa and 70 °C to 100 °C for 1.5 h to 2 h until no distillate was distilled off and the product was viscous. This yielded the hydroxyl-terminated hyperbranched polyester.

[0011] Another technical solution adopted in this invention is a method for preparing a high-strength membrane material based on bone glue, which is specifically implemented according to the following steps: Step 1: Weigh the following raw materials in parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium. Step 2: Immerse the bone glue in deionized water, allow it to swell, heat in a water bath, and stir continuously until the bone glue is completely dissolved to obtain a bone glue solution. Step 3: Add the hydroxyl-terminated hyperbranched polyester to the dispersion medium and stir to form a dispersion. Step 4: Prepare a film-forming solution using bone glue solution and terminal hydroxyl hyperbranched polyester dispersion; Step 5: Prepare a high-strength bone glue-based membrane material using a film-forming solution.

[0012] The invention is further characterized in that, In step 2, the swelling time is 12–24 h, and the water bath heating temperature is 40–50 ℃.

[0013] Step 4 specifically involves: Mix the bone glue solution with the hydroxyl-terminated hyperbranched polyester dispersion and stir for 10-15 min; then adjust the pH of the mixture to 8.0-9.5, heat the mixture in a 50-60 ℃ water bath for 20-40 min, and then sonicate it at 100-150 W and 40 kHz for 20-30 min to obtain a homogeneous film-forming solution.

[0014] Step 5 specifically involves: The film-forming solution is poured evenly onto a polytetrafluoroethylene mold, and the film thickness is controlled to be 0.1-0.3 mm. The mold is then placed in an oven at 40-50 ℃ and dried for 20-24 h. After drying, the mold is removed to obtain a bone glue-based high-strength film material.

[0015] The beneficial effects of this invention are: (1) The bone glue-based high-strength membrane material of the present invention uses bone glue as the base material and glycerol and maleic anhydride as raw materials. A terminal hydroxyl hyperbranched polyester is synthesized via esterification reaction as a modifying component to modify the bone glue base material, thus obtaining the bone glue-based high-strength membrane material. The resulting composite membrane material possesses excellent environmental friendliness and exhibits a certain degree of biodegradability in the natural environment.

[0016] (2) The bone glue-based high-strength membrane material of the present invention, by constructing a multi-hydrogen bond physical cross-linking network, simultaneously introduces hyperbranched structure and increases the free volume between molecular chains, to achieve a synergistic effect of reinforcement and toughening, so that the tensile strength of the membrane material is not less than 20 MPa and the elongation at break is maintained above 5%, which has both high strength and excellent flexibility; the stable intermolecular interaction inside the material can effectively avoid the performance degradation problem caused by the migration of small molecule plasticizers, and ensure the stability of the membrane material for long-term use.

[0017] (3) The bone glue-based high-strength film material of the present invention is prepared by casting film formation process. The reaction conditions are mild and no complicated special equipment is required. The preparation process is simple and can be widely used in agricultural films, packaging materials and other fields, which significantly expands the high-value application prospects of bone glue-based materials. Attached Figure Description

[0018] Figure 1 shows the stress-strain curves of BG / HBP, BG, and BG / Gly. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] The bone glue-based high-strength membrane material of the present invention comprises the following raw materials in parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium.

[0021] The bone glue used is high-purity bone glue with a protein content of ≥ 85% to ensure that it can be uniformly dispersed in the dispersion medium and form a continuous membrane structure; the dispersion medium is distilled water or deionized water to avoid the influence of impurities on membrane performance.

[0022] Hydroxyl-terminated hyperbranched polyesters are synthesized from glycerol and maleic anhydride via an esterification reaction. The synthesis steps are as follows: Glycerol and maleic anhydride were mixed in a molar ratio of 1:0.8-1.2 and reacted under nitrogen atmosphere at 70-80 °C for 1-2 h with stirring to ensure thorough mixing and esterification of the two monomers. Then, the reaction was carried out sequentially at 90-100 °C for 2 h, 110-120 °C for 2 h, and 130-140 °C for 3-5 h, gradually increasing the reaction temperature to promote the formation of branched structures. After the reaction was completed, nitrogen was continued to be introduced and the temperature was naturally cooled to 60-80 °C with stirring. Then, a neutralizing agent was added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the product was distilled under reduced pressure at -0.08 MPa to -0.095 MPa and 70 °C to 100 °C for 1.5 h to 2 h until no distillate was distilled off and the product was viscous. This yielded the hydroxyl-terminated hyperbranched polyester. The preparation method of the bone glue-based high-strength membrane material of the present invention is specifically implemented according to the following steps: Step 1: Weigh the following raw materials in parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium. The dispersion medium is distilled water or deionized water to avoid the influence of impurities on membrane performance.

[0023] Step 2: Immerse the bone glue in deionized water and allow it to swell at room temperature for 12–24 hours; then heat it in a water bath at 40–50 °C while continuously stirring until the bone glue is completely dissolved, resulting in a uniform, clear, viscous solution, which is the bone glue solution. Step 3: Add the hydroxyl-terminated hyperbranched polyester to the dispersion medium and stir continuously for 15-20 min to form a uniform and stable dispersion. Step 4: Mix the bone glue solution with the hydroxyl-terminated hyperbranched polyester dispersion and continue stirring for 10-15 min. Then adjust the pH of the mixture to 8.0-9.5 with 0.1 mol / L NaOH solution or 0.1 mol / L HCl solution. This pH range can promote the dissolution of bone glue protein and the stretching of molecular chains, which is beneficial for forming hydrogen bonds with the hydroxyl-terminated hyperbranched polyester. Place the pH-adjusted mixture in a 50-60 ℃ water bath and heat for 20-40 min to completely dissolve the bone glue. Then, sonicate it at 100-150 W and 40 kHz for 20-30 min to eliminate air bubbles and promote molecular-level mixing of bone glue and modifier to obtain a homogeneous film-forming solution. Step 5: Pour the film-forming liquid evenly onto the polytetrafluoroethylene mold, control the film thickness to be 0.1-0.3 mm, and dry it in an oven at 40-50 ℃ for 20-24 h. After taking it out, place it in a constant temperature and humidity desiccator at 25 ℃ and 50% relative humidity for 24 h to equilibrate and obtain the bone glue-based high-strength film material.

[0024] The present invention discloses a method for preparing a high-strength bone glue-based membrane material. Using glycerol and maleic anhydride as raw materials, a hydroxyl-terminated hyperbranched polyester is synthesized via esterification. This polyester is then compounded with bone glue through a solution blending-casting film-forming process to obtain the high-strength bone glue-based membrane material. The hydroxyl-terminated hyperbranched polyester forms multiple hydrogen bonds with the bone glue molecules, significantly improving the strength of the membrane material. Simultaneously, its highly branched three-dimensional spherical structure generates a large amount of free volume between molecular chains, effectively increasing the material's toughness and overcoming the problem of easy migration of traditional small-molecule plasticizers. The membrane material prepared by this invention uses biomass materials as the main raw material, exhibits a certain degree of biodegradability in the natural environment, has a tensile strength ≥ 20 MPa, and an elongation at break ≥ 5%, combining environmental friendliness and high performance, and can be applied in fields such as agricultural films and packaging materials.

[0025] Example 1 The preparation method of the bone glue-based high-strength membrane material of the present invention is specifically implemented according to the following steps: Weigh the following by weight: 5 parts bone glue, 1 part hydroxyl-terminated hyperbranched polyester, and 94 parts distilled water. Glycerol (0.5 mol, 46 g) and maleic anhydride (0.5 mol, 49 g) were added to a three-necked flask, nitrogen gas was introduced, and the mixture was stirred at 75 °C for 1 h. Subsequently, the mixture was reacted sequentially at 95 °C for 2 h, 115 °C for 2 h, and 135 °C for 4 h. After the reaction was completed, nitrogen gas was introduced again, and the mixture was allowed to cool naturally to 60 °C with stirring. A neutralizing agent was then added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the mixture was distilled under reduced pressure at -0.08 MPa and 70 °C for 1.5 h until no distillate was distilled off and the product was viscous. This yielded the hydroxyl-terminated hyperbranched polyester. Add 1 part of hydroxyl-terminated hyperbranched polyester to an appropriate amount of distilled water and stir at room temperature for 15 min to form a uniform dispersion. Five portions of bone glue were immersed in deionized water and allowed to swell at room temperature for 24 hours. Then, the solution was heated in a 40°C water bath and stirred continuously until the bone glue was completely dissolved, resulting in a uniform, clear, viscous solution. The bone glue solution was mixed with the hydroxyl-terminated hyperbranched polyester solution and stirred for 10 min. The pH was adjusted to 8.5 with 0.1 mol / L NaOH solution. The mixture was heated in a 50 ℃ water bath for 30 min, followed by ultrasonic emulsification at 120 W and 40 kHz for 25 min. The film-forming solution was poured into a 15 cm diameter polytetrafluoroethylene mold and dried in a 45 ℃ oven for 22 h. After drying, the film was equilibrated in a constant temperature and humidity desiccator for 24 h to obtain the membrane material.

[0026] Example 2 The preparation method of the bone glue-based high-strength membrane material of the present invention is specifically implemented according to the following steps: Weigh the following components by weight: 5 parts bone glue, 2.5 parts hydroxyl-terminated hyperbranched polyester, and 92.5 parts distilled water. Glycerol and maleic anhydride were mixed in a molar ratio of 1:0.8 and stirred at 70 °C under a nitrogen atmosphere for 1 h to ensure thorough mixing and esterification of the two monomers. The reaction was then carried out sequentially at 90 °C for 2 h, 110 °C for 2 h, and 130 °C for 3 h, gradually increasing the reaction temperature to promote the formation of branched structures. After the reaction was completed, nitrogen was continued to be introduced, and the temperature was naturally cooled to 80 °C while stirring. A neutralizing agent was then added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the product was distilled under reduced pressure at -0.095 MPa and 100 °C for 2 h until no distillate was distilled off and the product was viscous, thus obtaining the hydroxyl-terminated hyperbranched polyester. Add 2.5 parts of hydroxyl-terminated hyperbranched polyester to an appropriate amount of distilled water and stir at room temperature for 18 min to form a uniform dispersion. Five portions of bone glue were immersed in deionized water and allowed to swell at room temperature for 24 hours. Then, the solution was heated in a 40°C water bath and stirred continuously until the bone glue was completely dissolved, resulting in a uniform, clear, viscous solution. The bone glue solution was mixed with the hydroxyl-terminated hyperbranched polyester solution and stirred for 12 min. The pH was adjusted to 9.0 with 0.1 mol / L NaOH solution. The mixture was heated in a water bath at 55 ℃ for 35 min, followed by ultrasonic emulsification at 130 W and 40 kHz for 30 min. The film-forming solution was poured into a polytetrafluoroethylene mold with a diameter of 15 cm, dried in an oven at 45 ℃ for 24 h, and then equilibrated in a constant temperature and humidity desiccator for 24 h to obtain the membrane material.

[0027] Example 3 Weigh by weight: 8 parts bone glue, 4 parts hydroxyl-terminated hyperbranched polyester, and 88 parts distilled water; Glycerol and maleic anhydride were mixed in a molar ratio of 1:1.2 and stirred at 80 °C under a nitrogen atmosphere for 2 h to ensure thorough mixing and esterification of the two monomers. The reaction was then carried out sequentially at 100 °C for 2 h, 120 °C for 2 h, and 140 °C for 5 h, gradually increasing the reaction temperature to promote the formation of branched structures. After the reaction was completed, nitrogen gas was continuously introduced and the mixture was allowed to cool naturally to 60 °C while stirring. A neutralizing agent was then added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the mixture was distilled under reduced pressure at -0.095 MPa and 70 °C for 2 h until no distillate was distilled off and the product was viscous, thus obtaining the hydroxyl-terminated hyperbranched polyester. Add 4 parts of hydroxyl-terminated hyperbranched polyester to an appropriate amount of distilled water and stir at room temperature for 20 min to form a uniform dispersion. Eight portions of bone glue were immersed in deionized water and allowed to swell at room temperature for 24 hours; then heated in a 40 ℃ water bath and stirred continuously until the bone glue was completely dissolved, resulting in a uniform, clear, viscous solution. The bone glue solution was mixed with the hydroxyl-terminated hyperbranched polyester solution and stirred for 15 min. The pH was adjusted to 9.2 with 0.1 mol / L NaOH solution. The mixture was heated in a 60 ℃ water bath for 40 min, followed by ultrasonic emulsification at 150 W and 40 kHz for 28 min. The film-forming solution was poured into a 15 cm diameter polytetrafluoroethylene mold and dried in an oven at 48 ℃ for 23 h. After removal, it was equilibrated in a constant temperature and humidity desiccator for 24 h to obtain the membrane material.

[0028] Example 4 As a comparative experiment, glycerol-plasticized bone collagen membranes were prepared; Weigh the following ingredients by weight: 5 parts bone glue, 2.5 parts glycerin, and 92.5 parts distilled water; Five parts of bone glue were immersed in deionized water and allowed to swell at room temperature for 24 hours. Then, the solution was heated in a 40°C water bath and stirred continuously until the bone glue was completely dissolved, resulting in a uniform, clear, viscous solution. Two and a half parts of glycerol were added to the solution and stirred for 12 minutes. The pH was adjusted to 9.0 with 0.1 mol / L NaOH solution. Subsequent steps were the same as in Example 3.

[0029] Performance testing: Tensile strength 2.2 MPa, elongation at break 106.9%. The reasons are as follows: Glycerin, as a traditional small-molecule plasticizer, works by inserting into the spaces between collagen molecular chains, disrupting the original intermolecular forces and reducing the bonding force between molecular chains. The small-molecule plasticizer only forms weak interactions with collagen molecules, failing to build a stable cross-linked structure. This results in the membrane material being unable to resist external forces during stretching, manifesting as a significant decrease in tensile strength (only about 1 / 10 of the end-hydroxyl hyperbranched polyester modified collagen membrane material in this invention). The increased elongation at break is a direct manifestation of the plasticizing effect of glycerin. Small glycerin molecules fill the gaps between collagen molecular chains, increasing the free volume between molecular chains and reducing entanglement and aggregation caused by strong hydrogen bonds. The weak interactions make it easier for collagen molecular chains to slide and extend under stress, thus exhibiting a high elongation at break. However, this flexibility sacrifices its strength and long-term stability.

[0030] After 7 days of storage, glycerol precipitation caused stickiness on the membrane surface. This phenomenon is an inherent defect of small molecule plasticizers. The interaction between glycerol and collagen molecules is only a temporary weak hydrogen bond, lacking stable chemical bonding or dense physical cross-linking constraints. During room temperature storage, glycerol molecules gradually diffuse, migrate, and precipitate from the membrane interior to the surface due to concentration gradient and molecular thermal motion. Glycerol itself is viscous, and after precipitation, it adheres to the membrane surface, causing stickiness. At the same time, the loss of internal glycerol causes the collagen molecular chains to re-aggregate, which can lead to secondary brittleness of the membrane material and affect its performance.

[0031] Example 5 The hydroxyl-terminated hyperbranched polyester-reinforced modified bone glue base membrane material prepared in Example 3 was subjected to performance testing. Its tensile strength reached 22.6 MPa, and its elongation at break was 33.6%, which was about 15 times higher than that of pure bone glue membrane. The elongation at break was significantly better than that of pure bone glue membrane material. Compared with Example 4 (bone glue + glycerin plasticizer), its performance was "tensile strength 2.2 MPa". The tensile strength of the hydroxyl-terminated hyperbranched polyester-reinforced modified bone glue base membrane material was about 10 times higher than that of glycerin plasticized bone glue membrane.

[0032] The above method yields a high-strength bone glue-based membrane material that combines environmental friendliness and high performance, and can be applied to fields such as agricultural films and packaging materials.

[0033] The performance testing method in this invention is as follows: Tensile properties: According to ASTM D882-12 standard, a universal testing machine was used with a loading speed of 50 mm / min and a sample size of 100×10 mm. Three samples of each type were tested and the average value was taken.

[0034] Example 6 Figure 1 shows the stress-strain curves of hydroxyl-terminated hyperbranched polyester-modified bone glue membrane (BG / HBP), pure bone glue membrane (BG), and glycerol-modified bone glue membrane (BG / Gly). The horizontal axis represents strain (%), which is the elongation at break when the material is stretched. The larger the value, the stronger the toughness and flexibility of the material. The vertical axis represents stress (MPa), which is the tensile strength of the material against tensile failure. The larger the value, the stronger the material. Curve BG corresponds to the pure bone glue membrane, curve BG / HBP corresponds to the composite modified membrane of (bone glue + terminal hydroxyl hyperbranched polyester) in Example 3, and curve BG / Gly corresponds to the conventional plasticized modified membrane of the comparative example (bone glue + glycerol). As shown in the figure, the tensile strength (approximately 22.7 MPa) and elongation at break (approximately 33.7%) of the BG / HBP composite modified membrane are significantly better than those of the comparative example BG / Gly membrane (stress less than 3 MPa). At the same time, it overcomes the defect of the pure BG membrane having extremely poor toughness (strain < 2%), and achieves synergistic optimization of strength and toughness.

Claims

1. A high-strength membrane material based on bone glue, characterized in that, The raw materials include the following parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium; the dispersion medium is distilled water or deionized water; the hydroxyl-terminated hyperbranched polyester is synthesized by esterification reaction of glycerol and maleic anhydride.

2. The bone glue-based high-strength membrane material as described in claim 1, characterized in that, The synthesis steps of the terminal hydroxyl hyperbranched polyester are as follows: Glycerol and maleic anhydride in a molar ratio of 1:0.8-1.2 were mixed and reacted under nitrogen atmosphere at 70-80 °C for 1-2 h with stirring. Then, the reaction was carried out sequentially at 90-100 °C for 2 h, 110-120 °C for 2 h, and 130-140 °C for 3-5 h. After the reaction was completed, nitrogen was continued to be introduced and the temperature was naturally cooled to 60-80 °C with stirring. A neutralizing agent was then added to the system to adjust the acid value to ≤20 mg KOH / g. After washing with water to remove impurities, the product was distilled under reduced pressure at -0.08 MPa to -0.095 MPa and 70 °C to 100 °C for 1.5 h to 2 h until no distillate was distilled off and the product was viscous. This yielded the hydroxyl-terminated hyperbranched polyester.

3. The method for preparing the bone glue-based high-strength membrane material as described in claim 1, characterized in that, The specific steps are as follows: Step 1: Weigh the following raw materials in parts by weight: 5-10 parts bone glue, 1-5 parts hydroxyl-terminated hyperbranched polyester, and 85-95 parts dispersion medium. Step 2: Immerse the bone glue in deionized water, allow it to swell, heat in a water bath, and stir continuously until the bone glue is completely dissolved to obtain a bone glue solution. Step 3: Add the hydroxyl-terminated hyperbranched polyester to the dispersion medium and stir to form a dispersion. Step 4: Prepare a film-forming solution using bone glue solution and terminal hydroxyl hyperbranched polyester dispersion; Step 5: Prepare a high-strength bone glue-based membrane material using a film-forming solution.

4. The method for preparing the bone glue-based high-strength membrane material as described in claim 3, characterized in that, In step 2, the swelling time is 12–24 h, and the water bath heating temperature is 40–50 ℃.

5. The method for preparing the bone glue-based high-strength membrane material as described in claim 3, characterized in that, Step 4 specifically involves: Mix the bone glue solution with the hydroxyl-terminated hyperbranched polyester dispersion and stir for 10-15 min; then adjust the pH of the mixture to 8.0-9.5, heat the mixture in a 50-60 ℃ water bath for 20-40 min, and then sonicate it at 100-150 W and 40 kHz for 20-30 min to obtain a homogeneous film-forming solution.

6. The method for preparing the bone glue-based high-strength membrane material as described in claim 5, characterized in that, Use NaOH or HCl solution to adjust the pH of the mixture.

7. The method for preparing the bone glue-based high-strength membrane material as described in claim 3, characterized in that, Step 5 specifically involves: The film-forming solution is poured evenly onto a polytetrafluoroethylene mold, and the film thickness is controlled to be 0.1-0.3 mm. The mold is then placed in an oven at 40-50 ℃ and dried for 20-24 h. After drying, the mold is removed to obtain a bone glue-based high-strength film material.

8. The application of the bone glue-based high-strength film material as described in any one of claims 1-7 in agricultural films and packaging materials.

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