CN113637312A - Antibacterial material - Google Patents
Antibacterial material Download PDFInfo
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- CN113637312A CN113637312A CN202111015715.0A CN202111015715A CN113637312A CN 113637312 A CN113637312 A CN 113637312A CN 202111015715 A CN202111015715 A CN 202111015715A CN 113637312 A CN113637312 A CN 113637312A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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Abstract
The embodiment of the disclosure discloses an antibacterial material, which comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material. The embodiment of the disclosure provides a functional material with low density, high heat dissipation and antibacterial performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an antibacterial material.
Background
Resin materials are widely applied to electronic products, and have the characteristics of high strength and good temperature resistance, but the materials have large density, are not suitable for the development trend of light weight and high heat dissipation.
In order to achieve light weight and high heat dissipation, a resin material is modified by adding a low-density inorganic lightweight material thereto. However, the modification method by adding the low-density inorganic light filler can reduce the toughness of the material while realizing the reduction of the density and the improvement of the heat dissipation property, and the impact strength of the material is obviously reduced. In addition, nowadays, people gradually increase the antibacterial health care consciousness in the living environment, and in the electronic products and some application fields, the materials are required to have certain antibacterial performance, so that the materials can keep clean and sterile for a long time in use, and the breeding of harmful microorganisms is avoided.
Disclosure of Invention
The invention aims to provide a new technical scheme of an antibacterial material.
According to one aspect of the present invention, an antimicrobial material is provided. The antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material.
Optionally, the resin substrate includes any one of polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyetheretherketone, acrylonitrile-butadiene-styrene, or an alloy of at least two of the above materials.
Optionally, the additive comprises at least one of an antioxidant, a compatibilizer, a coupling agent, a light stabilizer, a lubricant, and a reinforcing agent.
Optionally, the compatibilizer comprises at least one of a maleic anhydride grafted acrylonitrile-styrene polymer, a polypropylene grafted maleic anhydride, and a maleic anhydride grafted ethylene-octene copolymer;
the coupling agent is a silane coupling agent;
the lubricant is calcium stearate;
the reinforcing agent is talcum powder.
Optionally, the antibacterial material comprises, by mass, 62-89 parts of the resin base material, 6-18 parts of the additive, and 5-15 parts of the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material.
Optionally, the preparation method of the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material comprises the following steps:
s101, mixing hollow glass beads with methanol, a silver nitrate aqueous solution and polyvinylpyrrolidone;
s102, adding an aqueous solution of sodium borohydride into the liquid obtained in the step S101, and mixing;
s103, adding ammonia water into the liquid obtained in the step S102 to obtain the amino modified hollow glass bead silver-loaded antibacterial agent;
s104, adding the carbon nano tube with the carboxylated surface into ethylene glycol, and uniformly dispersing;
and S105, adding the amino modified hollow glass bead silver-loaded antibacterial agent into the liquid obtained in the step S104, and performing radiant heating to enable carboxyl on the surface of the carbon nano tube subjected to surface carboxylation and amino on the surface of the amino modified hollow glass bead silver-loaded antibacterial agent to perform amidation reaction.
Optionally, the mass ratio of the carbon nanotubes with the carboxylated surfaces to the amino modified hollow glass bead silver-loaded antibacterial agent is 1-2: 1.
optionally, the method for preparing the surface-carboxylated carbon nanotube comprises the following steps:
mixing concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution;
adding carbon nanotubes into the mixed solution to perform an activation reaction;
wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3, the reaction temperature is 40-60 ℃, and the reaction time is 3-5 h.
Optionally, the volume ratio of the methanol to the aqueous solution of silver nitrate is 2: 1, the concentration of the ammonia water is 6 mol/L.
Optionally, in the step S104:
dispersing the carbon nano-tube with the carboxylated surface in ethylene glycol in an ultrasonic dispersion mode;
wherein the surface carboxylated carbon nano tube accounts for 2 to 10 percent of the total mass of the surface carboxylated carbon nano tube and the glycol.
According to the embodiment of the disclosure, the resin base material is modified by adding the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, so that the modified resin material has the characteristics of light weight and low density while the heat dissipation performance is improved, and also has an antibacterial function and good impact strength.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a flow chart of a method of preparing an antimicrobial material provided by an embodiment of the present disclosure;
FIG. 2 is a flow chart illustrating the preparation of surface carboxylated carbon nanotubes according to an embodiment of the present disclosure;
FIG. 3 is a flow chart of the preparation of the silver-loaded antibacterial agent of the amino-modified hollow glass beads provided by the embodiment of the disclosure.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The embodiment of the disclosure provides an antibacterial material, which comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material.
The resin base material has the characteristics of high strength and excellent temperature resistance.
The hollow glass beads belong to inorganic nonmetallic materials, and are usually nano, micron or micro-nano inorganic material spheres, and a hollow structure is formed inside the hollow glass beads. The hollow glass beads have the characteristics of light weight, good thermal stability and the like.
The hollow glass beads are a light material with excellent performance, and when the hollow glass beads are applied to the scheme disclosed by the disclosure, the weight of the resin base material can be reduced, so that the light weight effect of the material is achieved.
For example, the hollow glass beads are made of silica, alumina, zirconia, magnesia, sodium silicate, or the like.
After the hollow glass beads are loaded with silver, the hollow glass beads can be endowed with antibacterial and bacteriostatic effects.
Carbon Nanotubes (CNTs) have good elasticity, fatigue resistance, and isotropy, have very high hardness, comparable to diamond, and also have good flexibility and are stretchable. Moreover, the carbon nano tube has good heat transfer performance. The carbon nano tube has a very large length-diameter ratio, so that the heat exchange performance along the length direction of the carbon nano tube is high, the heat exchange performance in the vertical direction of the carbon nano tube is low, and the carbon nano tube can synthesize a high-anisotropy heat conduction material through proper orientation. The carbon nano tube has higher thermal conductivity, and the thermal conductivity of the material can be greatly improved as long as a trace amount of the carbon nano tube is doped in the material.
According to the embodiment of the disclosure, the resin base material is modified by adding the carboxylated carbon nanotube-loaded hollow glass bead-loaded silver composite material, so that the modified resin material has the characteristics of light weight and low density (namely light weight) while the heat dissipation performance is improved, and also has an antibacterial function and good impact strength.
The antibacterial material provided by the embodiment of the disclosure can be applied to the field of electronic products.
Wherein the resin base material is, for example, a thermoplastic resin material.
In some examples of the present disclosure, the resin substrate includes any one of polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyether ether ketone, acrylonitrile-butadiene-styrene, or an alloy material of at least two of the above materials.
In the embodiment of the present disclosure, the additive is added to the resin base material and mixed uniformly, which can be used to improve the properties of the material, such as temperature resistance, durability, etc., according to the type of the additive.
For example, the additive includes at least one of an antioxidant, a compatibilizer, a coupling agent, a light stabilizer, a lubricant, and a reinforcing agent.
Wherein the compatilizer is maleic anhydride grafted compatilizer.
The maleic anhydride grafted compatilizer enables the material to have high polarity and reactivity by introducing strong polar reactive groups, can greatly improve the compatibility and the dispersibility of the composite material, and is favorable for uniformly dispersing the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material in the resin base material.
In some examples of the present disclosure, the compatibilizer includes at least one of a maleic anhydride grafted acrylonitrile-styrene polymer, a polypropylene grafted maleic anhydride, and a maleic anhydride grafted ethylene-octene copolymer.
And an antioxidant is added into the resin base material, so that the thermal oxidation degradation of the material in a long-term aging process can be prevented.
In some examples of the present disclosure, the antioxidant is antioxidant 1010 (chemical name: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]).
The antioxidant 1010 is a phenol antioxidant, and after the phenol antioxidant is applied to a resin base material, the antioxidant performance of the material can be improved, and the service life of a resin product can be effectively prolonged. Moreover, the antioxidant 1010 has the advantages of small volatility, high thermal stability, long lasting effect, no pollution and no toxicity.
Wherein the coupling agent is, for example, a silane coupling agent, such as silane coupling agent KH 550.
As another example, the coupling agent is KH 792.
The silane coupling agent is added into the resin base material, so that the dispersibility and the adhesive force of the filler in the resin can be improved, and the compatibility between the inorganic filler and the resin can be improved.
Wherein the lubricant is, for example, calcium stearate.
The calcium stearate has excellent lubricating properties, and can be used as a lubricant and a mold release agent.
Wherein the reinforcing agent is talcum powder.
Wherein the type of the light stabilizer is 944.
In the related art, the resin material is generally made lightweight by adding micro-foaming. However, the mechanical properties of the resin material are reduced by the micro-foaming method, and the process is complicated, and the bubble control is a technical problem.
According to the scheme, the modified resin material which is light in weight, low in density, high in heat dissipation and antibacterial can be prepared by adopting the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material which is low in density, high in heat dissipation and antibacterial, combining the additive and mixing the additive with the resin base material. Moreover, the prepared material can meet the mechanical property of the material while realizing light weight, and has good impact strength.
According to the antibacterial material provided by the embodiment of the disclosure, the resin base material is 62-89 parts by mass, the additive is 6-18 parts by mass, and the carboxylated carbon nanotube-loaded hollow glass bead-loaded silver composite material is 5-15 parts by mass. Wherein, the material of the resin base material is the above listed material, and the specific type of the additive can be flexibly selected according to specific situations. The resin base material can be modified by adding the carboxylated carbon nanotube-loaded hollow glass bead-loaded silver composite material, so that the heat dissipation performance of the resin base material is improved, and the resin base material has the characteristic of light weight and also has an antibacterial function.
In an embodiment of the present disclosure, as shown in fig. 2 and 3, a preparation method of the carboxylated carbon nanotube-supported hollow glass bead-supported silver composite material includes:
s101, mixing the hollow glass beads with methanol, a silver nitrate aqueous solution and polyvinylpyrrolidone.
The using amount of the methanol and the silver nitrate is determined according to the using amount of the hollow glass microspheres.
In some examples of the disclosure, the volume ratio of the methanol to the aqueous solution of silver nitrate is 2: 1.
the silver nitrate is a silver source.
The polyvinylpyrrolidone (PVP) is a non-ionic polymer, belonging to N-vinyl amide polymer, and contains
The group, here, acts as a dispersant.
In some examples of the present disclosure, 500mg of the hollow glass microspheres (e.g., having a particle size of 10 μm to 250 μm) were mixed with 20ml of the methanol, 10ml of the aqueous solution of silver nitrate, and an appropriate amount of polyvinylpyrrolidone PVP, and stirred for 6 hours in the absence of light.
And S102, adding the aqueous solution of sodium borohydride into the liquid obtained in the step S101, and mixing.
And slowly dropping the aqueous solution of sodium borohydride into the liquid obtained in the step S101 at a constant speed, and slowly stirring for reaction for 30min to fully react.
Sodium borohydride is an inorganic substance with the chemical formula of NaBH4It is used as a reducing agent. Sodium borohydride is readily soluble in methanol.
And S103, adding ammonia water into the liquid obtained in the step S102 to obtain the amino modified hollow glass bead silver-loaded antibacterial agent.
The concentration of the aqueous ammonia is controlled to 6mol/L, for example.
And adding ammonia water into the liquid obtained in the step S102, continuing stirring and reacting for 10min, and then centrifugally settling, washing and drying to finally obtain the amino modified hollow glass bead silver-loaded antibacterial agent.
Taking 500mg of cenospheres in the step S101 as an example, the concentration of the ammonia water is 6mol/L, and the adding amount of the ammonia water is, for example, 5ml to 10 ml.
And S104, adding the carbon nano tube with the carboxylated surface into ethylene glycol, and uniformly dispersing.
The preparation method of the carbon nano tube with the carboxylated surface comprises the following steps:
mixing concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution;
adding carbon nanotubes into the mixed solution to perform an activation reaction;
wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3, the reaction temperature is 40-60 ℃, and the reaction time is 3-5 h.
The concentrated sulfuric acid is sulfuric acid having a concentration of 98% or more, and the concentrated nitric acid is nitric acid having a concentration of 63% or more.
In the step S104:
dispersing the carbon nano-tube with the carboxylated surface in ethylene glycol in an ultrasonic dispersion mode;
wherein the surface carboxylated carbon nano tube accounts for 2 to 10 percent of the total mass of the surface carboxylated carbon nano tube and the glycol.
And S105, adding the amino modified hollow glass bead silver-loaded antibacterial agent into the liquid obtained in the step S104, and performing radiant heating to enable carboxyl on the surface of the carbon nano tube subjected to surface carboxylation and amino on the surface of the amino modified hollow glass bead silver-loaded antibacterial agent to perform amidation reaction.
The mass ratio of the carbon nano tubes with the carboxylated surfaces to the amino modified hollow glass bead silver-loaded antibacterial agent is 1-2: 1.
the method is characterized in that a microwave method is adopted for heating by utilizing heat radiation, and carboxyl on the surface of a carbon nano tube and amino on the surface of a hollow glass microsphere silver-loaded antibacterial agent are subjected to amidation reaction, and the method specifically comprises the following steps:
the carboxyl on the surface of the carbon nano tube and the amino on the surface of the hollow glass microsphere silver-loaded antibacterial agent are subjected to amidation reaction by adopting a microwave method and utilizing radiation heating, so that the carbon nano tube loaded glass microsphere silver-loaded composite material is prepared. The problems of uneven mixing and unobvious weight reduction, heat dissipation and antibacterial effects in the mixing of the three fillers are solved.
According to a second embodiment of the present disclosure, there is provided a method of preparing the above resin material, including: as shown in fig. 1, the carboxylated carbon nanotube-supported hollow glass bead silver-loaded composite material and the additive are added into the resin base material, stirred uniformly and then granulated.
In some examples of the disclosure, a mixture of the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, an additive and a resin base material is added into a high-speed mixer, wherein the resin base material accounts for 62-89 parts by mass, the additive accounts for 6-18 parts by mass, the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material accounts for 5-15 parts by mass, and after uniform mixing, the mixture is extruded and granulated by a double-screw extruder at an extrusion temperature of 270 ℃.
The preparation process disclosed by the invention is simple, low in cost and easy for large-scale production.
According to the antibacterial material prepared by the method, the resin base material is modified by adding the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, so that the modified resin material has the characteristics of light weight and low density (namely light weight) while the heat dissipation performance is improved, and also has an antibacterial function and better mechanical performance.
Example 1
The antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material are added into the resin base material, the resin base material is polycarbonate and is 89 parts, the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material is 5 parts, and the additive comprises 1.5 parts of antioxidant 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH 550.
Example 2
The antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material are added into the resin base material, the resin base material is polycarbonate and is 84 parts, the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material is 10 parts, and the additive comprises 1.5 parts of antioxidant 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH 550.
Example 3
The antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material are added into the resin base material, the resin base material is polycarbonate and is 79 parts, the carboxylated carbon nanotube loaded hollow glass microsphere silver-loaded composite material is 15 parts, and the additive comprises 1.5 parts of antioxidant 1010, 2.5 parts of maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of silane coupling agent KH 550.
The above-mentioned examples 1 to 3 are low-density high-heat-dissipation antibacterial polycarbonate resin materials.
Comparative example 1
A resin material comprises a resin base material and an additive, wherein the additive is added into the resin base material, the resin base material is polycarbonate and is 94 parts, and the additive comprises 1.5 parts of an antioxidant 1010, 2.5 parts of a maleic anhydride grafted acrylonitrile-styrene polymer and 2 parts of a silane coupling agent KH 550.
In comparative example 1, the carboxylated carbon nanotube-supported hollow glass bead-supported silver composite material was not added.
The processing techniques of examples 1-3, and comparative example 1 are as follows:
adding the mixture into a high-speed mixer, uniformly mixing, and extruding and granulating by using a double-screw extruder under the condition that the extrusion temperature is 270 ℃.
Example 4
An antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material, the resin base material is PA6 polyamide and 77 parts, the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material is 5 parts, and the additive comprises 1 part of a light stabilizer 944, 2 parts of an antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of a silane coupling agent KH 550.
Example 5
An antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material, the resin base material is PA6 polyamide and is 72 parts, the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material is 10 parts, and the additive comprises 1 part of a light stabilizer 944, 2 parts of an antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of a silane coupling agent KH 550.
Example 6
An antibacterial material comprises a resin base material, an additive and a carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material are added into the resin base material, the resin base material is PA6 polyamide and is 67 parts, the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material is 15 parts, and the additive comprises 1 part of a light stabilizer 944, 2 parts of an antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of a silane coupling agent KH 550.
Examples 4 to 6 described above are low-density high-heat-dissipation antibacterial PA6 polyamide resin materials.
Comparative example 2
A resin material comprises a resin base material and an additive, wherein the additive is added into the resin base material, the resin base material is PA6 polyamide and is 82 parts, and the additive comprises 1 part of light stabilizer 944, 2 parts of antioxidant 1010, 6 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 7 parts of maleic anhydride grafted ethylene-octene copolymer and 2 parts of silane coupling agent KH 550.
In comparative example 2, the carboxylated carbon nanotube-loaded hollow glass bead-loaded silver composite material was not added.
The processing techniques of examples 4-6, and comparative example 2 are as follows:
adding the mixture into a high-speed mixer, uniformly mixing, and extruding and granulating by using a double-screw extruder under the condition that the extrusion temperature is 275 ℃.
Example 7
The utility model provides an antibacterial material, includes resin substrate, additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite, the additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is added to in the resin substrate, wherein, the resin substrate is polypropylene and is 84 parts, carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is 5 parts, the additive includes 1 part antioxidant 1010, 1 part calcium stearate, 5 parts talcum powder, 2 parts polypropylene grafting maleic anhydride (PP-g-MAH) and 2 parts coupling agent KH 792.
Example 8
The utility model provides an antibacterial material, includes resin substrate, additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite, the additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is added to in the resin substrate, wherein, the resin substrate is polypropylene and is 79 parts, carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is 10 parts, the additive includes 1 part of antioxygen 1010, 1 part of calcium stearate, 5 parts of talcum powder, 2 parts of polypropylene grafting maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH 792.
Example 9
The utility model provides an antibacterial material, includes resin substrate, additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite, the additive and carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is added to in the resin substrate, wherein, the resin substrate is polypropylene and is 74, carboxylated carbon nanotube load hollow glass microballon silver-carrying composite is 15, the additive includes 1 part of antioxygen 1010, 1 part of calcium stearate, 5 parts of talcum powder, 2 parts of polypropylene grafting maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH 792.
The above-mentioned examples 7 to 9 are low-density high-heat-dissipation antibacterial polypropylene resin materials.
Comparative example 3
A resin material comprises a resin base material and an additive, wherein the additive is added into the resin base material, the resin base material is polypropylene and is 89 parts, and the additive comprises 1 part of antioxidant 1010, 1 part of calcium stearate, 5 parts of talcum powder, 2 parts of polypropylene grafted maleic anhydride (PP-g-MAH) and 2 parts of coupling agent KH 792.
In comparative example 3, the carboxylated carbon nanotube-loaded hollow glass bead-loaded silver composite material was not added.
The processing techniques of examples 7-9, and comparative example 3 are as follows:
adding the mixture into a high-speed mixer, uniformly mixing, and extruding and granulating by using a double-screw extruder under the condition that the extrusion temperature is 200 ℃.
The density, mechanical properties and antibacterial properties of the products of examples 1 to 9, and the products of comparative examples 1 to 3 are shown in table 1.
TABLE 1
The method for detecting the bacteriostatic rate of escherichia coli and staphylococcus aureus comprises the following steps:
1. at least 3 pieces of the antibacterial material in each example were prepared as test pieces. At least 6 pieces of the material to which no antibacterial component was added, that is, the material in each comparative example were prepared as samples, 3 pieces of the sample to which no antibacterial component was added were used for measuring the number of viable bacteria immediately after inoculation of the strain, and the other 3 pieces were used for measuring the number of viable bacteria 24 hours after inoculation.
2. Each sample was prepared into a disk having a diameter of 40mm and a thickness of 5 mm. The samples were placed individually in sterile petri dishes with the test side facing up. 0.4ml of the inoculum was pipetted and dropped onto the surface of each sample. And covering a film which is prepared in advance and has the diameter of 35mm on the inoculated bacterial liquid, and slightly pressing the film downwards to enable the bacterial liquid to diffuse towards the periphery so as to ensure that the bacterial liquid does not overflow from the edge of the film. After the sample is inoculated and covered with the film, the culture dish cover is covered again.
3. The culture dish was incubated at 35 ℃ and 90% humidity. For the samples containing no antibacterial component, the number of bacteria was measured immediately after inoculation, and viable bacteria count was performed 24 hours after the remaining samples.
The bacteriostasis rate is 1- (viable bacteria/total bacteria) 100
After the carboxylated carbon nanotube loaded hollow glass bead silver-loaded composite material is modified, the density of the resin material is obviously reduced, the notch impact strength is kept at a good level, the structural strength requirement of a product can be met, and meanwhile, the heat dissipation performance and the antibacterial property are in an obvious increasing trend.
With reference to the QBT2591-2003 standard, an antibacterial plastic with a bacteriostasis rate of 99% or more can report a strong antibacterial effect, and an antibacterial plastic with an antibacterial rate of 90% or more can report an antibacterial effect. The antibacterial product disclosed by the invention has a bacteriostasis rate of more than 99.9% on escherichia coli and a bacteriostasis rate of more than 99.9% on staphylococcus aureus, and has a strong antibacterial effect.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The antibacterial material is characterized by comprising a resin base material, an additive and a carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material, wherein the additive and the carboxylated carbon nanotube-loaded hollow glass microsphere silver-loaded composite material are added into the resin base material.
2. The antimicrobial material of claim 1, wherein the resin substrate comprises any one of polycarbonate, polypropylene, polyethylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyetheretherketone, acrylonitrile-butadiene-styrene, or an alloy of at least two of the foregoing materials.
3. The antimicrobial material of claim 1, wherein the additive comprises at least one of an antioxidant, a compatibilizer, a coupling agent, a light stabilizer, a lubricant, and a reinforcing agent.
4. The antimicrobial material of claim 3, wherein the compatibilizer comprises at least one of a maleic anhydride grafted acrylonitrile-styrene polymer, a polypropylene grafted maleic anhydride, and a maleic anhydride grafted ethylene-octene copolymer;
the coupling agent is a silane coupling agent;
the lubricant is calcium stearate;
the reinforcing agent is talcum powder.
5. The antibacterial material according to claim 1, wherein the resin base material is 62-89 parts by mass, the additive is 6-18 parts by mass, and the carboxylated carbon nanotube-loaded hollow glass microsphere-loaded silver composite material is 5-15 parts by mass.
6. The antibacterial material of claim 1, wherein the preparation method of the carboxylated carbon nanotube-supported hollow glass bead-supported silver composite material comprises the following steps:
s101, mixing hollow glass beads with methanol, a silver nitrate aqueous solution and polyvinylpyrrolidone;
s102, adding an aqueous solution of sodium borohydride into the liquid obtained in the step S101, and mixing;
s103, adding ammonia water into the liquid obtained in the step S102 to obtain the amino modified hollow glass bead silver-loaded antibacterial agent;
s104, adding the carbon nano tube with the carboxylated surface into ethylene glycol, and uniformly dispersing;
and S105, adding the amino modified hollow glass bead silver-loaded antibacterial agent into the liquid obtained in the step S104, and performing radiant heating to enable carboxyl on the surface of the carbon nano tube subjected to surface carboxylation and amino on the surface of the amino modified hollow glass bead silver-loaded antibacterial agent to perform amidation reaction.
7. The antibacterial material according to claim 6, wherein the mass ratio of the surface-carboxylated carbon nanotubes to the silver-loaded amino-modified hollow glass bead antibacterial agent is 1-2: 1.
8. the antimicrobial material of claim 6, wherein the surface-carboxylated carbon nanotubes are prepared by a method comprising:
mixing concentrated sulfuric acid and concentrated nitric acid to obtain a mixed solution;
adding carbon nanotubes into the mixed solution to perform an activation reaction;
wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3, the reaction temperature is 40-60 ℃, and the reaction time is 3-5 h.
9. The antimicrobial material of claim 6, wherein the volume ratio of the methanol to the aqueous solution of silver nitrate is 2: 1, the concentration of the ammonia water is 6 mol/L.
10. The antibacterial material according to claim 6, wherein in the step S104:
dispersing the carbon nano-tube with the carboxylated surface in ethylene glycol in an ultrasonic dispersion mode;
wherein the surface carboxylated carbon nano tube accounts for 2 to 10 percent of the total mass of the surface carboxylated carbon nano tube and the glycol.
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