CN112175369B - High-fluidity medical antibacterial degradable composite material and preparation method thereof - Google Patents

Abstract

The invention discloses a high-fluidity medical antibacterial grade degradable composite material, which comprises, by weight, 50-85 parts of a degradable material, 0.2-2 parts of an antibacterial agent, 3-5 parts of a compatilizer, 0.2-1 part of peroxide and 0.1-1 part of an antioxidant, wherein the peroxide is an organic peroxide. In the technical scheme, the composite material with better degradability, fluidity and toughness is obtained by controlling the melt index and the proportion of the degradable material. The antibacterial property and the compatibility of the whole material can be better improved by adding the antibacterial agent and the compatilizer, so that the composite material has better mechanical property while having better antibacterial property and compatibility.

Description

A kind of high fluidity medical antibacterial grade degradable composite material and preparation method thereof

technical field

The application belongs to the technical field of degradable composite materials, and in particular relates to a high-fluidity medical antibacterial-grade degradable composite material and a preparation method thereof.

Background technique

Degradable materials, also known as biodegradable materials, refer to the degradation caused by the action of microorganisms existing in nature such as bacteria, molds, fungi and algae in nature, such as composting conditions, anaerobic digestion conditions or aqueous culture solutions, and eventually completely Materials that degrade into carbon dioxide, methane, water, and mineralized inorganic salts of the elements they contain, as well as new biomass. With the rapid growth of the population, the consumption of medical supplies is also increasing year by year, especially the use of disposable protective medical supplies such as masks is also increasing sharply. Existing masks are basically composed of inner, middle and outer layers. The inner layer is generally skin-friendly gauze or non-woven fabric, the middle layer is generally polypropylene meltblown cloth, and the outer layer is polypropylene meltblown cloth with antibacterial effect. . However, polypropylene is a refractory polymer material. It needs to exist in nature for hundreds of years before it can be slowly degraded. The long-term existence of polypropylene in nature will have a greater impact on the environment. Degradable composites of materials.

SUMMARY OF THE INVENTION

In order to solve the above technical problems, the first aspect of the present invention provides a high-fluidity medical antibacterial grade degradable composite material, the raw materials of which include 50-85 parts of degradable materials, 0.2-2 parts of antibacterial agent, and 3 parts of compatibilizer. -5 parts, 0.2-1 part of peroxide and 0.1-1 part of antioxidant, the peroxide is an organic peroxide.

Preferably, the degradable material is selected from at least one of polylactic acid, polybutylene succinate, polyhydroxyalkanoate, polyethylene succinate, polypropylene carbonate and polyglycolic acid kind.

Preferably, the melt index of the degradable material is 8-80 g/10min.

Preferably, the antibacterial agent is a silver antibacterial agent and/or a zinc antibacterial agent.

Preferably, the silver antibacterial agent is a silver ion antibacterial agent.

Preferably, the zinc-based antibacterial agent is nano-zinc oxide.

Preferably, the compatibilizer is selected from amide compounds, silane coupling agents, titanate coupling agents, aluminate coupling agents, oxoate coupling agents, bimetallic coupling agents, rare earth coupling agents , at least one of phosphorus-containing coupling agent and boron-containing coupling agent.

Preferably, the amide compound is oleic acid amide and/or erucic acid amide.

Preferably, the organic peroxide is selected from di-tert-butyl peroxide, tert-butyl-1,1,3,3-tetramethylbutyl peroxide, dicumyl peroxide, tertiary At least one of butyl isopropyl peroxide and 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide.

A second aspect of the present invention provides a method for preparing a high-fluidity medical antibacterial-grade degradable composite material, comprising at least the following steps:

(1) mixing the degradable material, antibacterial agent, compatibilizer, peroxide and antioxidant to obtain mixture A;

(2) Melting and extruding the mixture A through a screw extruder, cooling and dicing to obtain a high-fluidity medical antibacterial agent degradable composite material.

Beneficial effects: In the technical scheme, by controlling the melt index and proportion of the degradable material, a composite material with good degradability, fluidity and toughness is obtained. The inventor found that by adding a certain proportion of silver antibacterial agent and zinc antibacterial agent, not only the antibacterial performance of the whole material can be improved, but also the anti-discoloration performance and stability of the whole material can be improved. Moreover, the inventor unexpectedly found that adding a certain proportion of titanate coupling agent and amide compound can not only improve the compatibility of the antibacterial agent in the overall material, but also improve the fluidity and mechanical properties of the overall material. It also enables the overall material to have long-term lubricating properties.

Detailed ways

For the purposes of the following detailed description, it should be understood that the present invention may employ various alternative variations and sequences of steps, unless expressly stated to the contrary. Furthermore, except in any working example, or where otherwise indicated, all numbers expressing amounts of ingredients, eg, as used in the specification and claims, should be understood to be modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At least not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, but each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values of the range, and every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. Furthermore, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein. For example, a specified range from "1 to 10" should be deemed to include any and all subranges between a minimum value of 1 and a maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

In order to solve the above technical problems, the first aspect of the present invention provides a high-fluidity medical antibacterial-grade degradable composite material, in parts by weight, the raw materials include 50-85 parts of degradable materials, 0.2-2 parts of antibacterial agents , 3-5 parts of a compatibilizer, 0.2-1 part of a peroxide and 0.1-1 part of an antioxidant, wherein the peroxide is an organic peroxide.

As a preferred technical solution, the degradable material is selected from polylactic acid, polybutylene succinate, polyhydroxyalkanoate, polyethylene succinate, polypropylene carbonate and polyethanol at least one of acids.

As a preferred technical solution, the melt index of the degradable material is 8-80 g/10min.

As a more preferred technical solution, the degradable material is a mixture of polylactic acid, polybutylene succinate and polyhydroxyalkanoate, and the polylactic acid, polybutylene succinate and polyhydroxyalkanoate The mass ratio of hydroxy fatty acid ester is 3:1:2.

As a more preferred technical solution, the melt index of the polylactic acid is 80g/10min, at 210°C, 2.16Kg, and obtained by testing according to ASTM D1238, and the brand name is NatureWorks, 75168.

As a more preferred technical solution, the melt index of the polybutylene succinate is 25g/10min, at 210 ° C, 2.16Kg, obtained by testing with reference to ASTM D1238, purchased from Jinan Xinweida Chemical Co., Ltd., The grade is TH804.

As a more preferred technical solution, the melt index of the polyhydroxyalkanoate is 8g/10min, at 210°C, 2.16Kg, obtained by testing with reference to ASTM D1238, purchased from Dongguan Yuefa Plastic Materials Co., Ltd., and the trade name is EM10050.

Polylactic acid is a biodegradable material, which is a high-concentration lactic acid produced by saccharification of starch raw materials through saccharification, and then fermented with glucose and certain strains of high-concentration lactic acid, and then chemically synthesized. Polylactic acid has good biodegradability and can be completely degraded by microorganisms in nature, eventually generating carbon dioxide and water, without polluting the environment, which is very beneficial to protecting the environment and is recognized as an environmentally friendly material. And polylactic acid has good thermal stability, biocompatibility and good ductility, but the inventors found that polylactic acid is more brittle. Polybutylene succinate is easily decomposed and metabolized by microorganisms in nature or enzymes in animals and plants, and finally decomposed into carbon dioxide and water. It is a typical fully biodegradable polymer material. With good biocompatibility and bioabsorbability, polybutylene succinate has good toughness and processing properties. Polyhydroxyalkanoates have good biodegradability and biocompatibility. The inventor unexpectedly found that by controlling the melt index of polylactic acid and adding a certain amount of polybutylene succinate and polyhydroxyalkanoate, it can be completely degraded, flexible, biocompatible, brittle. Smaller and more liquid products. The inventor believes that the possible reason is that the addition of polybutylene succinate and polyhydroxyalkanoate increases the degree of randomness between the shorter polylactic acid molecular chains, and the obtained composite material has a better biological phase. Compatibility and toughness, less brittleness and higher fluidity, but the inventors found that the antibacterial properties of the prepared composites were poor.

As a preferred technical solution, the antibacterial agent is a silver antibacterial agent and/or a zinc antibacterial agent.

As a preferred technical solution, the silver antibacterial agent is a silver ion antibacterial agent.

As a preferred technical solution, the zinc-based antibacterial agent is nano-zinc oxide.

As a preferred technical solution, the antibacterial agent is a mixture of silver ion antibacterial agent and nano-zinc oxide, and the mass ratio of the silver ion antibacterial agent and nano-zinc oxide is 1:(1-3).

As a more preferred technical solution, the particle size of the nano-zinc oxide is 30 nm, which is obtained by using transmission electron microscope observation method, and is purchased from Nanjing Poket New Materials Co., Ltd., article number: PZT.

The inventor found that by adding silver ion antibacterial agent, the composite material can obtain better antibacterial effect. The silver ion antibacterial agent can fully contact with bacteria and enter its interior, combine with the sulfhydryl group of bacterial oxygen metabolism enzyme, and make bacterial respiratory metabolism. blocked, killing bacteria. However, the inventor found that adding silver ion antibacterial agent is easy to cause discoloration of the material. The inventor unexpectedly found that a certain proportion of silver ion antibacterial agent mixed with nano-zinc oxide can play a better antibacterial effect, and the overall composite material will not change color. The inventor believes that the possible reason is that when the nano-zinc oxide is irradiated by light with energy greater than its forbidden band width, the electrons in the valence band are excited to transition to the conduction band, leaving positively charged holes, electrons and electrons in the valence band. The holes will be adsorbed on the surface of the material by reactants such as oxygen, hydroxyl and water to generate oxygen negative ions. The oxygen negative ions generated by nano-zinc oxide have high reducing ability, which can prevent the oxidation of silver ion antibacterial agents, so that the overall composite material has a relatively high performance. While the antibacterial effect is good, the overall composite material will not be discolored, and the stability of the overall composite material will be improved.

As a preferred technical solution, the compatibilizer is selected from amide compounds, silane coupling agents, titanate coupling agents, aluminate coupling agents, oxoate coupling agents, and bimetallic coupling agents , at least one of rare earth coupling agent, phosphorus-containing coupling agent and boron-containing coupling agent.

As a preferred technical solution, the amide compounds are oleic acid amide and/or erucic acid amide.

As a preferred technical solution, the compatibilizer is a mixture of a titanate coupling agent and an amide compound, and the mass ratio of the titanate coupling agent to the amide compound is 15:1.

The inventors found that adding more amide compounds can improve the compatibility, fluidity and lubricity of the overall material. But at the same time, the inventors found that adding more amide compounds has a great influence on the mechanical properties of the overall material, which will reduce the mechanical properties of the overall material.

The inventor unexpectedly found that by adding a certain proportion of titanate coupling agent and amide compound, the overall composite material can have better compatibility, fluidity, long-term lubricity and better mechanical properties. The inventor believes that the possible reason is that the amide compound can reduce the force between the polymer molecular chains, so that a smaller gap can be generated between the molecular chains, so that the silver ion antibacterial agent particles and the nano-zinc oxide particles can be better fused. Into the polymer, and can improve the fluidity of the overall material, but it will lead to the decline of the mechanical properties of the overall material, the amide compound easily migrates to the surface of the composite material, and cannot maintain long-term compatibilization and lubrication. The titanate coupling agent can not only play a good compatibilizing effect, but also can transesterify with polyesters, which can further improve the mechanical properties of the overall material. The molecular force is large, which can effectively reduce the migration of amide compounds, so that the overall material maintains good compatibility, fluidity, mechanical properties and long-term lubrication.

As a preferred technical solution, the organic peroxide is selected from di-tert-butyl peroxide, tert-butyl-1,1,3,3-tetramethylbutyl peroxide, dicumyl At least one of peroxide, tert-butyl isopropyl peroxide and 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

Organic peroxides can degrade polymer segments and effectively improve the fluidity of the overall material.

A second aspect of the present invention provides a method for preparing a high-fluidity medical antibacterial-grade degradable composite material, comprising at least the following steps:

(1) mixing the degradable material, antibacterial agent, compatibilizer, peroxide and antioxidant to obtain mixture A;

(2) Melting and extruding the mixture A through a screw extruder, cooling and dicing to obtain a high-fluidity medical antibacterial agent degradable composite material.

In addition, all raw materials used are commercially available unless otherwise stated.

Example

Example 1

The first aspect of this embodiment provides a high-fluidity medical antibacterial-grade degradable composite material, in parts by weight, the raw materials include 50 parts of degradable materials, 0.2 parts of antibacterial agent, 3 parts of compatibilizer, peroxide 0.2 parts of organic peroxides and 0.1 parts of antioxidants, the peroxides are organic peroxides.

The degradable material is a mixture of polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester, and the mass ratio of the polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester is 3 :1:2.

The polylactic acid has a melt index of 80g/10min, 2.16Kg at 210°C, and is obtained by testing according to ASTM D1238, and the brand name is NatureWorks, 75168.

The melt index of the polybutylene succinate is 25g/10min, at 210° C., 2.16Kg, obtained by testing with reference to ASTMD1238, purchased from Jinan Xinweida Chemical Co., Ltd., and the trade name is TH804.

The melt index of the polyhydroxyalkanoate is 8g/10min, at 210°C, 2.16Kg, and obtained by testing according to ASTM D1238, and it was purchased from Dongguan Yuefa Plastic Materials Co., Ltd. under the brand name EM10050.

The antibacterial agent is a mixture of silver ion antibacterial agent and nano-zinc oxide, and the mass ratio of the silver ion antibacterial agent and nano-zinc oxide is 1:3. The silver ion antibacterial agent was purchased from Dongguan Aimeier Antifungal Antibacterial Technology Co., Ltd., item number: ADM-Ag08.

The particle size of the nano-zinc oxide is 30 nm, which is obtained by using the transmission electron microscope observation method, and is purchased from Nanjing Poket New Material Co., Ltd., item number: PZT.

The compatibilizer is a mixture of a titanate coupling agent and an amide compound, and the mass ratio of the titanate coupling agent to the amide compound is 15:1. Described titanate coupling agent is isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, and the trade mark of described isopropyl tris (dioctyl pyrophosphate acyloxy) titanate is: American Kenridge KR-38S. The amide compound is oleic acid amide, and the oleic acid amide was purchased from Jiangxi Zhilian Plastic Chemical Technology Co., Ltd., CAS number: 301-02-0.

The organic peroxide is 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide, and the organic peroxide is purchased from Xingbeida (Beijing) Chemical Materials Co., Ltd., and the trade name is: Aksu double 25. The antioxidant is antioxidant 1010.

A second aspect of this embodiment provides a method for preparing a high-fluidity medical antibacterial-grade degradable composite material, comprising the following steps:

(1) Polylactic acid, polybutylene succinate, polyhydroxyalkanoate, silver ion antibacterial agent, nano-zinc oxide, isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, oil Acid amide, 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide and antioxidant 1010 are mixed to obtain mixture A;

(2) Melting and extruding the mixture A through a screw extruder, cooling and dicing to obtain a high-fluidity medical antibacterial agent degradable composite material.

Example 2

The first aspect of this embodiment provides a high-fluidity medical antibacterial-grade degradable composite material, in parts by weight, the raw materials include 85 parts of degradable materials, 2 parts of antibacterial agent, 5 parts of compatibilizer, peroxide 1 part of organic peroxide and 1 part of antioxidant, the peroxide is organic peroxide.

The degradable material is a mixture of polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester, and the mass ratio of the polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester is 3 :1:2.

The polylactic acid has a melt index of 80g/10min, 2.16Kg at 210°C, and is obtained by testing according to ASTM D1238, and the brand name is NatureWorks, 75168.

The melt index of the polybutylene succinate is 25g/10min, at 210° C., 2.16Kg, obtained by testing with reference to ASTMD1238, purchased from Jinan Xinweida Chemical Co., Ltd., and the trade name is TH804.

The melt index of the polyhydroxyalkanoate is 8g/10min, at 210°C, 2.16Kg, and obtained by testing according to ASTM D1238, and it was purchased from Dongguan Yuefa Plastic Materials Co., Ltd. under the brand name EM10050.

The antibacterial agent is a mixture of silver ion antibacterial agent and nano-zinc oxide, and the mass ratio of the silver ion antibacterial agent and nano-zinc oxide is 1:3. The silver ion antibacterial agent was purchased from Dongguan Aimeier Antifungal Antibacterial Technology Co., Ltd., item number: ADM-Ag08.

The particle size of the nano-zinc oxide is 30 nm, which is obtained by using the transmission electron microscope observation method, and is purchased from Nanjing Poket New Material Co., Ltd., item number: PZT.

The compatibilizer is a mixture of a titanate coupling agent and an amide compound, and the mass ratio of the titanate coupling agent to the amide compound is 15:1. Described titanate coupling agent is isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, and the trade mark of described isopropyl tris (dioctyl pyrophosphate acyloxy) titanate is: American Kenridge KR-38S. The amide compound is erucamide, and the erucamide was purchased from Jiangxi Zhilian Plastic & Chemical Technology Co., Ltd., CAS number: 112-84-5.

The organic peroxide is 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide, and the organic peroxide is purchased from Xingbeida (Beijing) Chemical Materials Co., Ltd., and the trade name is: Aksu double 25. The antioxidant is antioxidant 1010.

A second aspect of this embodiment provides a method for preparing a high-fluidity medical antibacterial-grade degradable composite material, comprising the following steps:

(1) Polylactic acid, polybutylene succinate, polyhydroxyalkanoate, silver ion antibacterial agent, nano-zinc oxide, isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, mustard Acid amide, 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide and antioxidant 1010 are mixed to obtain mixture A;

(2) Melting and extruding the mixture A through a screw extruder, cooling and dicing to obtain a high-fluidity medical antibacterial agent degradable composite material.

Example 3

The first aspect of this embodiment provides a high-fluidity medical antibacterial-grade degradable composite material, in parts by weight, the raw materials include 60 parts of degradable materials, 0.4 parts of antibacterial agent, 3.2 parts of compatibilizer, peroxide 0.3 parts of organic peroxides and 0.2 parts of antioxidants, the peroxides are organic peroxides.

The degradable material is a mixture of polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester, and the mass ratio of the polylactic acid, polybutylene succinate and polyhydroxy fatty acid ester is 3 :1:2.

The polylactic acid has a melt index of 80g/10min, 2.16Kg at 210°C, and is obtained by testing according to ASTM D1238, and the brand name is NatureWorks, 75168.

The melt index of the polybutylene succinate is 25g/10min, at 210° C., 2.16Kg, obtained by testing with reference to ASTMD1238, purchased from Jinan Xinweida Chemical Co., Ltd., and the trade name is TH804.

The melt index of the polyhydroxyalkanoate is 8g/10min, at 210°C, 2.16Kg, and obtained by testing according to ASTM D1238, and it was purchased from Dongguan Yuefa Plastic Materials Co., Ltd. under the brand name EM10050.

The antibacterial agent is a mixture of silver ion antibacterial agent and nano-zinc oxide, and the mass ratio of the silver ion antibacterial agent and nano-zinc oxide is 1:3. The silver ion antibacterial agent was purchased from Dongguan Aimeier Antifungal Antibacterial Technology Co., Ltd., item number: ADM-Ag08.

The particle size of the nano-zinc oxide is 30 nm, which is obtained by using the transmission electron microscope observation method, and is purchased from Nanjing Poket New Material Co., Ltd., item number: PZT.

The compatibilizer is a mixture of a titanate coupling agent and an amide compound, and the mass ratio of the titanate coupling agent to the amide compound is 15:1. Described titanate coupling agent is isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, and the trade mark of described isopropyl tris (dioctyl pyrophosphate acyloxy) titanate is: American Kenridge KR-38S. The amide compound is oleic acid amide, and the oleic acid amide was purchased from Jiangxi Zhilian Plastic Chemical Technology Co., Ltd., CAS number: 301-02-0.

The organic peroxide is 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide, and the organic peroxide is purchased from Xingbeida (Beijing) Chemical Materials Co., Ltd., and the trade name is: Aksu double 25. The antioxidant is antioxidant 1010.

A second aspect of this embodiment provides a method for preparing a high-fluidity medical antibacterial-grade degradable composite material, comprising the following steps:

(1) Polylactic acid, polybutylene succinate, polyhydroxyalkanoate, silver ion antibacterial agent, nano-zinc oxide, isopropyl tris (dioctyl pyrophosphate acyloxy) titanate, oil Acid amide, 2,5-dimethyl-2,5-di-tert-butyl hexane peroxide and antioxidant 1010 are mixed to obtain mixture A;

(2) Melting and extruding the mixture A through a screw extruder, cooling and dicing to obtain a high-fluidity medical antibacterial agent degradable composite material.

Comparative Example 1

The difference between this comparative example and Example 1 is that the degradable material in this example is a mixture of polylactic acid, polybutylene succinate and polyhydroxyalkanoate. The mass ratio of acid butylene glycol ester and polyhydroxyalkanoate is 3:1:2.

The melt index of the polylactic acid is 7g/10min, at 210° C., 2.16Kg, according to the test of ASTM D1238, and the brand name is NatureWorks, 75168.

The melt index of the polybutylene succinate is 7g/10min, at 210° C., 2.16Kg, obtained by testing with reference to ASTMD1238, purchased from Jinan Xinweida Chemical Co., Ltd., and the brand name is TH802A.

The melt index of the polyhydroxyalkanoate is 5g/10min, at 210° C., 2.16Kg, according to ASTM D1238, and it was purchased from Dongguan Yuefa Plastic Materials Co., Ltd. under the trade name EM10080.

Comparative Example 2

The difference between this comparative example and Example 1 is that the antibacterial agent in this example is a silver ion antibacterial agent, and the silver ion antibacterial agent is purchased from Dongguan Aimeier Antifungal Antibacterial Technology Co., Ltd., article number: ADM- Ag08.

Comparative Example 3

The difference between this comparative example and Example 1 is that the antibacterial agent in this example is nano-zinc oxide, and the particle size of the nano-zinc oxide is 30 nm, which is obtained by using transmission electron microscope observation method, and purchased from Nanjing Baokite New Materials Co., Ltd., Article No.: PZT.

Comparative Example 4

The difference between this comparative example and Example 1 is that the compatibilizer in this example is isopropyl tris(dioctyl pyrophosphate acyloxy) titanate, the isopropyl tris(dioctyl The grade of pyrophosphate acyloxy) titanate is: American Kenridge KR-38S.

Comparative Example 5

The difference between this comparative example and Example 1 is that the compatibilizer in this example is oleic acid amide, and the oleic acid amide is purchased from Jiangxi Zhilian Plastics Technology Co., Ltd., CAS No.: 301-02- 0.

Performance Testing

1. Degradation rate test

According to GB/T 19277.1-2011 "Determination of the final aerobic biodegradability of materials under controlled composting conditions using the method for measuring the released carbon dioxide", the high-fluidity medical antibacterial grade degradable composites prepared in the examples and comparative examples were determined. 6-month degradation rate of material composting.

2. Melt index test

At 210°C, 2.16Kg, refer to ASTM D1238 to test the melt index of the high-flow medical antibacterial-grade degradable composite materials obtained in the examples and comparative examples.

3. Anti-migration test

10 samples of the high-fluidity medical antibacterial-grade degradable composite materials prepared in the examples and the comparative examples were respectively injection-molded and placed in an oven at 35°C for 100 hours. Afterwards, the surface of the samples was observed to see if they became embossed, and the migration resistance of the materials was evaluated. , observe whether discoloration occurs, and evaluate the stability performance. 0-1 samples have excellent resistance to migration, 2-5 samples have good migration resistance, 6-10 samples have poor migration resistance, 0 -1 sample has excellent discoloration stability, 2-5 samples have good discoloration stability, and 6-10 samples have poor discoloration stability.

4. Specific gravity test

According to GB1033-1986 "Plastic Density and Relative Density Test Method" standard, the specific gravity of the high-fluidity medical antibacterial-grade degradable composite materials prepared in the examples and comparative examples is determined, and the specific gravity is 1.10-1.18g/ ^cm3 is qualified, otherwise Failed.

5. Antibacterial effect

According to GB15979-2002 "Hygienic Standard for Disposable Sanitary Products", the antibacterial properties of the high-fluidity medical antibacterial-grade degradable composite materials obtained in the examples and comparative examples were determined, and the antibacterial properties of the total number of bacterial colonies were less ^than 200cfu/m2. Qualified, the total number of bacterial colonies greater than 200cfu/ ^m2 antibacterial performance is unqualified.

It can be seen from the above data that in this technical solution, by controlling the melt index and proportion of the degradable material, a composite material with good degradability, fluidity and toughness is obtained. Adding a certain proportion of titanate coupling agent and amide compound can not only improve the compatibility of the antibacterial agent in the overall material, but also improve the flow effect, long-term lubricating performance and mechanical properties of the overall material.

The above are only preferred embodiments of the present invention, and are not intended to limit the invention in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or change to equivalent implementations of equivalent changes. For example, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (3)

1. The high-fluidity medical antibacterial grade degradable composite material is characterized by comprising, by weight, 50-85 parts of a degradable material, 0.2-2 parts of an antibacterial agent, 3-5 parts of a compatilizer, 0.2-1 part of peroxide and 0.1-1 part of an antioxidant, wherein the peroxide is an organic peroxide; the degradable material is a mixture of polylactic acid, poly butylene succinate and polyhydroxyalkanoate, and the mass ratio of the polylactic acid to the poly butylene succinate to the polyhydroxyalkanoate is 3: 1: 2; the compatilizer is a mixture of a titanate coupling agent and an amide compound, and the mass ratio of the titanate coupling agent to the amide compound is 15: 1;

the melt index of the polylactic acid is 80g/10min, and the polylactic acid is obtained by testing at 210 ℃ and 2.16Kg according to ASTM D1238;

the melt index of the poly (butylene succinate) is 25g/10min, and the poly (butylene succinate) is obtained by testing at 210 ℃ and 2.16Kg according to ASTM D1238;

the polyhydroxyalkanoate has a melt index of 8g/10min, and is measured at 210 ℃ and 2.16Kg according to ASTM D1238;

the antibacterial agent is a mixture of a silver ion antibacterial agent and nano zinc oxide;

the mass ratio of the silver ion antibacterial agent to the nano zinc oxide is 1: 3;

the amide compound is oleamide and/or erucamide.

2. The high flow medical antimicrobial grade degradable composite material of claim 1 wherein the organic peroxide is selected from at least one of di-t-butyl peroxide, t-butyl-1, 1, 3, 3-tetramethylbutyl peroxide, diisopropylphenyl peroxide, t-butylisopropyl peroxide, and 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane.

3. A method for preparing the high-fluidity medical antibacterial grade degradable composite material according to any one of claims 1 to 2, which comprises at least the following steps:

(1) mixing a degradable material, an antibacterial agent, a compatilizer, peroxide and an antioxidant to obtain a mixture A;

(2) and melting and extruding the mixture A through a screw extruder, cooling and granulating to obtain the high-fluidity degradable medical antibacterial agent composite material.