Biodegradable antibacterial material and application

Abstract

The invention relates to the technical field of high polymer materials, particularly discloses a biodegradable antibacterial material, and also discloses an application of the biodegradable antibacterial material. According to the biodegradable antibacterial material provided by the invention, the biodegradable resin PBAT is modified by adopting the nano xylan bacteriostatic agent, so that the material is endowed with excellent antibacterial activity, the physical property of the obtained material is improved, the production cost is reduced, and the high-strength biodegradable antibacterial material is obtained.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a biodegradable antibacterial material, as well as the application of this biodegradable antibacterial material. Background Technology

[0002] With the development of science and technology, many polymer materials are applied to all aspects of society, but the resulting white pollution problem urgently needs to be solved. Therefore, it is imperative to develop biodegradable materials to replace the widely used plastics and spinning materials.

[0003] The most widely used biodegradable material on the market is PBAT (polybutylene terephthalate), which is modified by the action of starch and plasticizers. The resulting modified product is white in color and has good physical properties, such as tensile strength and toughness. However, the current modified material is mainly used in low-priced daily necessities such as supermarket shopping bags and straws, that is, its application is limited to the most basic packaging field, thus restricting its application scope.

[0004] Antibacterial materials have become a major highlight in the field of materials science in recent years. By adding antibacterial agents, materials can be endowed with antibacterial properties, thereby broadening their application areas. For example, patent document CN115651376A discloses an antibacterial material that modifies biodegradable resins (PBAT, PLA) by adding antibacterial agents, resulting in an antibacterial material with excellent barrier properties.

[0005] The present invention aims to develop a new biodegradable antibacterial material that, while adding antibacterial properties to the material, further enhances the material's physical properties, thus providing a biodegradable material with excellent physical properties. Summary of the Invention

[0006] The main technical problem solved by this invention is to provide a biodegradable antibacterial material, and also to provide the application of this biodegradable antibacterial material. This biodegradable antibacterial material has excellent antibacterial properties, good physical properties, and high strength.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a biodegradable antibacterial material, wherein the antibacterial material comprises the following raw materials in parts by weight: 60-70 PBATs 2-10 parts of rigid biodegradable polymer 15-22 parts of inorganic filler 1-8 parts of antibacterial agent; The antibacterial agent is a nano-xylan antibacterial agent, which is prepared by the following method: S1: Sorbitol, citric acid and xylose are mixed and then stirred to react, resulting in xylan; The reaction temperature is 85-95℃, and the mass ratio of xylose, sorbitol, and citric acid is (16-20):(5-8):1; preferably, the mass ratio of xylose, sorbitol, and citric acid is 18:6:1. S2: The xylan obtained in step S1 is reacted with an alkali, wherein the alkali is sodium hydroxide, and 200 ml of sodium hydroxide aqueous solution is added for every 1 g of xylan. The mass percentage concentration of the sodium hydroxide aqueous solution is 10-40%, preferably 15-25%. The pH of the reaction system was then adjusted to 5.5-7.0, and ethanol was added for alcohol precipitation. The ethanol used was a 95% ethanol solution. A precipitate was formed after the ethanol was added. Then, solid-liquid separation is performed, for example, by centrifugation to collect the precipitate, followed by filtration. The resulting solid product is the nano-xylan antibacterial agent.

[0008] As one embodiment of the present invention, the raw materials for preparing the antibacterial material further include 0.5-2 parts by weight of 1,4-butanediol (BDO).

[0009] As one embodiment of the present invention, the raw materials for preparing the antibacterial material further include 0.01-0.2 parts by weight of an antihydrolysis agent.

[0010] As one embodiment of the present invention, the raw materials for preparing the antibacterial material further include 0.2-0.25 parts by weight of a chain extender.

[0011] As one embodiment of the present invention, the raw materials for preparing the antibacterial material further include 0.3-0.5 parts by weight of lubricant.

[0012] In one embodiment of the present invention, the weight-average molecular weight of the PBAT is 100,000-150,000.

[0013] As one embodiment of the present invention, the rigid biodegradable polymer is PLA (polylactic acid) and / or PBS (polybutylene succinate).

[0014] In one embodiment of the present invention, the inorganic filler is starch and / or calcium carbonate.

[0015] As one embodiment of the present invention, the anti-hydrolysis agent is selected from at least one of BIO362, SW100, and 768.

[0016] As one embodiment of the present invention, the chain extender is selected from one or more of epoxy chain extenders, isocyanate chain extenders, and trioxazoline chain extenders.

[0017] As one embodiment of the present invention, the lubricant is selected from one or more of vinyl bis-stearamide, zinc stearate, calcium stearate, erucamide, polyethylene wax, stearic acid, montan wax, rice bran wax, and mono- and diglyceride fatty acid esters.

[0018] This invention provides a method for preparing the biodegradable antibacterial material of the present invention, comprising the steps of: mixing PBAT, rigid biodegradable polymer, inorganic filler, anti-hydrolysis agent, chain extender, lubricant, and antibacterial agent, and feeding the mixture into the main feed port of a twin-screw extruder for co-mixing, shearing, extrusion, and granulation to obtain the biodegradable antibacterial material.

[0019] This invention provides another method for preparing the biodegradable antibacterial material described in this invention, comprising the steps of: mixing PBAT, rigid biodegradable polymer, inorganic filler, anti-hydrolysis agent, chain extender, lubricant, antibacterial agent, and 1,4-butanediol, and feeding the mixture into the main feed port of a twin-screw extruder for co-blending, shearing, extrusion, and granulation to obtain the biodegradable antibacterial material.

[0020] The present invention also provides an application of the biodegradable antibacterial material described herein, including applications in biodegradable medical materials and biodegradable antibacterial packaging materials.

[0021] The biodegradable antibacterial material provided by this invention uses a nano-xylan antibacterial agent obtained through biomass refining to modify the biodegradable resin PBAT. While imparting excellent antibacterial properties to the material, the nano-xylan antibacterial agent itself also possesses good plasticizing properties, thus simultaneously improving the physical properties of the modified material and reducing production costs. By adding BDO to the raw materials, the melt flow index of the material can be significantly increased while maintaining the physical properties, meeting the needs of spinning in medical material applications and enabling its manufacture into medical sutures, etc. Furthermore, by adding rigid biodegradable polymers such as PLA to the raw materials, the strength of the material can be improved, meeting application requirements. This high-strength, biodegradable antibacterial material provided by this invention greatly expands the application fields of existing biodegradable materials, and can be used in areas including biodegradable medical materials and biodegradable antibacterial packaging materials.

[0022] The biodegradable antibacterial material provided by this invention uses PBAT, the main raw material, which has excellent biodegradability and is environmentally friendly. By modifying PBAT with starch, nano-xylan antibacterial agents, and other raw materials, the material cost is significantly reduced, and it exhibits excellent human compatibility, perfectly solving the compatibility problem of existing medical antibacterial materials. Furthermore, the biodegradability of this antibacterial material effectively solves the waste disposal problem. Attached Figure Description

[0023] Figure 1This is a comparison diagram of the inhibition zones of the biodegradable antibacterial material provided in Example 2 of the present invention and the blank control group; The left figure shows the inhibition zone of the blank control group, and the right figure shows the inhibition zone of the biodegradable antibacterial material provided in Example 2. Detailed Implementation

[0024] The technical solution of the present invention will be described in detail below through specific embodiments. These embodiments are intended to further illustrate the content of the present invention, but are not intended to limit the scope of protection of the claims of the present invention.

[0025] This invention provides a biodegradable antibacterial material, and the raw materials used in its preparation are as follows by weight: 60-70 PBATs 2-10 parts of rigid biodegradable polymer 15-22 parts of inorganic filler 1-8 parts of antibacterial agent 0.5-2 parts of 1,4-Butanediol (BDO) Anti-hydrolysis agent 0.01-0.2 parts Chain extender 0.2-0.25 parts 0.3-0.5 parts of lubricant.

[0026] Furthermore, the present invention provides a biodegradable antibacterial material, wherein the raw materials are prepared in the following weight proportions: PBAT 62-70 copies 2-8 parts of rigid biodegradable polymer 20-22 parts of inorganic filler 1-3 parts of antibacterial agent 0.5-1 part of 1,4-Butanediol (BDO) Anti-hydrolysis agent 0.01-0.1 parts Chain extender 0.2-0.25 parts 0.3-0.5 parts of lubricant.

[0027] This invention provides another biodegradable antibacterial material, the raw materials for which are prepared in the following weight proportions: 60-70 PBATs 2-10 parts of rigid biodegradable polymer 15-22 parts of inorganic filler 1-8 parts of antibacterial agent Anti-hydrolysis agent 0.01-0.2 parts Chain extender 0.2-0.25 parts 0.3-0.5 parts of lubricant.

[0028] Furthermore, the present invention provides a biodegradable antibacterial material, wherein the raw materials are prepared in the following weight proportions: PBAT 62-70 copies 2-8 parts of rigid biodegradable polymer 20-22 parts of inorganic filler 1-3 parts of antibacterial agent Anti-hydrolysis agent 0.01-0.1 parts Chain extender 0.2-0.25 parts 0.3-0.5 parts of lubricant.

[0029] In this invention, the PBAT used has a weight-average molecular weight of 100,000-150,000 and a melt index of 3-6 g / 10 min (190 °C, 2.16 kg).

[0030] The rigid biodegradable polymers used are PLA (polylactic acid) and / or PBS (polybutylene succinate).

[0031] The inorganic filler used is starch and / or calcium carbonate.

[0032] The anti-hydrolysis agent used is selected from at least one of BIO362, SW100, and 768.

[0033] The chain extender used is selected from one or more of epoxy chain extenders, isocyanate chain extenders, and trioxazoline chain extenders.

[0034] The lubricant used is selected from one or more of the following: vinyl bis-stearamide, zinc stearate, calcium stearate, erucamide, polyethylene wax, stearic acid, montan wax, rice bran wax, and mono- and diglyceride fatty acid esters.

[0035] Specifically, in the following embodiments and comparative examples: The PBAT used was KHB21AP11 produced by Kanghui New Materials, with a weight-average molecular weight of approximately 130,000 and a melt index of 3.6 g / 10 min (190℃, 2.16 kg).

[0036] The rigid biodegradable polymer used was PLA, specifically KHB22AP11 produced by Kanghui Company, with a melt index of 3.5 g / 10 min (190℃, 2.16 kg).

[0037] The inorganic filler is starch 2160.

[0038] The anti-hydrolysis agent is 768 (Beijia Fine Chemicals).

[0039] The chain extender is epoxy chain extender KL-4370B, purchased from Shanxi Chemical Research Institute, with an epoxy equivalent of 270-430 g / mol and a molecular weight of 6000-7000.

[0040] The lubricant is polyethylene wax and erucamide.

[0041] The antibacterial agent used is a nano-xylan antibacterial agent, which is prepared by the following method: S1: Sorbitol, citric acid and xylose are mixed and then stirred to react to obtain xylan; wherein the reaction temperature is 90℃ and the mass ratio of xylose, sorbitol and citric acid is 18:6:1; S2: The xylan obtained in step S1 is reacted with sodium hydroxide. For every 1g of xylan, 200ml of sodium hydroxide aqueous solution is added. The mass percentage concentration of the sodium hydroxide aqueous solution is 20%. Then adjust the pH value to 6.5, and then add 95% ethanol for alcohol precipitation to obtain a precipitate. Then centrifuge to collect the precipitate, and then filter the collected precipitate to collect the solid. The obtained solid product is the nano xylan antibacterial agent.

[0042] The biodegradable antibacterial material provided by this invention is obtained by mixing various raw materials and feeding them into the main feed port of a twin-screw extruder for co-mixing, shearing, extrusion, and granulation.

[0043] The twin-screw extruder has a temperature of 135-175℃, a rotation speed of 160-250rpm, and a feeding speed of 2.5-3.5Hz.

[0044] Unless otherwise specified, all reagents used in the following examples and comparative examples are commercially available products.

[0045] Unless otherwise specified, the experimental methods used in the following examples and comparative examples are conventional experimental methods.

[0046] Example 1 This embodiment provides a biodegradable antibacterial material, and the weight proportions of the raw materials used in its preparation are as follows: PBAT 69.4 copies PLA 2 copies 216,022 parts starch 2 parts of nano-xylan antibacterial agent 7680.1 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts of lubricant.

[0047] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0048] The method for preparing the biodegradable antibacterial material provided in this embodiment includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-165℃, the screw speed is 210 rpm, and the feed speed is 2.5 Hz. Specifically, the temperature in zones one to three of the extruder is 135-165℃, the temperature in zones four to eight is 160℃, and the temperature in zones nine to twelve is 160-165℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable antibacterial material are obtained.

[0049] Example 2 This embodiment provides a biodegradable antibacterial material, and the weight proportions of the raw materials used in its preparation are as follows: PBAT 63.4 copies PLA8 copies 216,022 parts starch 2 parts of nano-xylan antibacterial agent 7680.05 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts of lubricant.

[0050] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0051] The method for preparing the biodegradable antibacterial material provided in this embodiment includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-175℃, the screw speed is 200 rpm, and the feed speed is 2.5 Hz. The temperature of zones one to three of the extruder is 135-165℃, the temperature of zones four to eight is 170℃, and the temperature of zones nine to twelve is 170-175℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable antibacterial material are obtained.

[0052] Example 3 This embodiment provides a biodegradable antibacterial material, and the weight proportions of the raw materials used in its preparation are as follows: PBAT 68.4 copies PLA 2 copies 216,022 parts starch 2 parts of nano-xylan antibacterial agent 7680.1 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts lubricant 1 part of 1,4-butanediol.

[0053] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0054] The method for preparing the biodegradable antibacterial material provided in this embodiment includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-165℃, the screw speed is 210 rpm, and the feed speed is 2.5 Hz. Specifically, the temperature in zones one to three of the extruder is 135-165℃, the temperature in zones four to eight is 160℃, and the temperature in zones nine to twelve is 160-165℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable antibacterial material are obtained.

[0055] Example 4 This embodiment provides a biodegradable antibacterial material, and the weight proportions of the raw materials used in its preparation are as follows: PBAT 62.4 copies PLA8 copies 216,022 parts starch 2 parts of nano-xylan antibacterial agent 7680.1 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts lubricant 1 part of 1,4-butanediol.

[0056] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0057] The method for preparing the biodegradable antibacterial material provided in this embodiment includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-175℃, the screw speed is 200 rpm, and the feed speed is 2.5 Hz. The temperature of zones one to three of the extruder is 135-165℃, the temperature of zones four to eight is 170℃, and the temperature of zones nine to twelve is 170-175℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable antibacterial material are obtained.

[0058] Comparative Example 1 This comparative example provides a biodegradable material, and the weight parts of the raw materials used in its preparation are as follows: PBAT 63.4 copies PLA8 copies 216,022 parts starch 7680.05 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts of lubricant.

[0059] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0060] The method for preparing the biodegradable material provided in this comparative example includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-175℃, the screw speed is 200 rpm, and the feed speed is 2.5 Hz. The temperature in zones one to three of the extruder is 135-165℃, the temperature in zones four to eight is 170℃, and the temperature in zones nine to twelve is 170-175℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable material are obtained.

[0061] Comparative Example 2 This comparative example provides a biodegradable material, and the weight parts of the raw materials used in its preparation are as follows: PBAT 62.4 copies PLA8 copies 216,022 parts starch 7680.1 parts of anti-hydrolysis agent 0.2 parts of epoxy chain extender KL-4370B 0.4 parts lubricant 1 part of 1,4-butanediol.

[0062] The lubricant is a mixture of polyethylene wax and erucamide in a 1:1 mass ratio.

[0063] The method for preparing the biodegradable material provided in this comparative example includes the following steps: All the above raw materials are fed into a high-speed mixer and mixed evenly. Then, the mixture is fed into the main feed port of a twin-screw extruder. The extruder processing temperature is 135-175℃, the screw speed is 200 rpm, and the feed speed is 2.5 Hz. The temperature in zones one to three of the extruder is 135-165℃, the temperature in zones four to eight is 170℃, and the temperature in zones nine to twelve is 170-175℃. After air cooling, pelletizing, and drying, extruded chips of the biodegradable material are obtained.

[0064] Performance testing The biodegradable materials prepared in Examples 1-4 and Comparative Examples 1-2 were tested, and the test methods for the relevant performance indicators are as follows: Melt flow index: Tested according to GB / T3682 test method.

[0065] Antibacterial performance: The test was conducted according to GB / T 38483-2020 "Determination of Antibacterial Activity of Secondary Metabolites of Microbial Antibiotics - Inhibition Zone Method". The specific steps were as follows: tryptone, yeast, sodium chloride, and agar were weighed, dissolved by boiling, and the pH was adjusted to neutral. The mixture was then sterilized at high temperature for 30 minutes to prepare LB medium. An environmentally friendly bacterial suspension was inoculated onto the medium and incubated at 37℃ for 12 hours. The suspension was then evenly spread using a bead-drop method. Finally, an appropriate amount of sample solution was added dropwise to the medium, and the mixture was incubated at 37℃ for 12 hours. The results were then observed. The blank control group consisted of medium without the addition of sample solution.

[0066] Tensile strength: Tested according to GB / T 1040.3-2006 test method.

[0067] Toughness: Tested according to GB / T 1040.3-2006 test method.

[0068] Table 1 below shows the test results for each embodiment and comparative example.

[0069] Table 1 As shown in Table 1 above, the biodegradable antibacterial materials provided in Examples 1-4 of this invention have a tensile strength > 20 MPa, an antibacterial rate > 99%, good physical properties, and good antibacterial performance.

[0070] The inhibition zone diagrams of the biodegradable antibacterial material provided in Example 2 of this invention and the blank control group are shown below. Figure 1 As shown in the figure, the antibacterial properties of the biodegradable antibacterial material provided in Example 2 of the present invention are significantly improved.

[0071] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent transformations made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A biodegradable antibacterial material, characterized in that, The antibacterial material comprises the following raw materials in parts by weight: 60-70 PBATs 2-10 parts of rigid biodegradable polymer 15-22 parts of inorganic filler 1-8 parts of antibacterial agent; The antibacterial agent is a nano-xylan antibacterial agent, which is prepared by the following method: S1: Sorbitol, citric acid and xylose are mixed and then stirred to react, resulting in xylan; S2: The xylan obtained in step S1 is reacted with alkali, and then the pH value is adjusted to 5.5-7.

0. After that, ethanol is added for alcohol precipitation, and then solid-liquid separation is performed. The solid product obtained is the nano-xylan antibacterial agent.

2. The biodegradable antibacterial material according to claim 1, characterized in that, The raw materials for preparing the antibacterial material also include 0.5-2 parts by weight of 1,4-butanediol.

3. The biodegradable antibacterial material according to claim 1 or 2, characterized in that, The raw materials for preparing the antibacterial material also include 0.01-0.2 parts by weight of an antihydrolysis agent.

4. The biodegradable antibacterial material according to claim 1 or 2, characterized in that, The raw materials for preparing the antibacterial material also include 0.2-0.25 parts by weight of chain extender.

5. The biodegradable antibacterial material according to claim 1 or 2, characterized in that, The raw materials for preparing the antibacterial material also include 0.3-0.5 parts by weight of lubricant.

6. The biodegradable antibacterial material according to claim 1 or 2, characterized in that, The weight-average molecular weight of the PBAT is 100,000-150,000; and / or, The rigid biodegradable polymer is PLA and / or PBS; and / or, The inorganic filler is starch and / or calcium carbonate.

7. The biodegradable antibacterial material according to claim 3, characterized in that, The anti-hydrolysis agent is selected from at least one of BIO362, SW100, and 768.

8. The biodegradable antibacterial material according to claim 4, characterized in that, The chain extender is selected from one or more of epoxy chain extenders, isocyanate chain extenders, and trioxazoline chain extenders.

9. The biodegradable antibacterial material according to claim 5, characterized in that, The lubricant is selected from one or more of vinyl bis-stearamide, zinc stearate, calcium stearate, erucamide, polyethylene wax, stearic acid, montan wax, rice bran wax, and mono- and diglyceride fatty acid esters.

10. The application of the biodegradable antibacterial material according to any one of claims 1-9 in biodegradable medical materials and biodegradable antibacterial packaging materials.

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