CN112063065A - Preparation method of polyethylene wax-based nano-silver antibacterial material and application of polyethylene wax-based nano-silver antibacterial material in polyethylene injection molding products - Google Patents

Preparation method of polyethylene wax-based nano-silver antibacterial material and application of polyethylene wax-based nano-silver antibacterial material in polyethylene injection molding products Download PDF

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CN112063065A
CN112063065A CN202010817393.0A CN202010817393A CN112063065A CN 112063065 A CN112063065 A CN 112063065A CN 202010817393 A CN202010817393 A CN 202010817393A CN 112063065 A CN112063065 A CN 112063065A
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polyethylene wax
polyethylene
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antibacterial material
silver antibacterial
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CN112063065B (en
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林辉
吴院生
吴峰
简露琴
钱浩
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Xiamen Toppla Material Technology Co ltd
Xiamen Make Security Technology Co Ltd
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    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/08Copolymers of ethene
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Abstract

The invention discloses a preparation method of a polyethylene wax-based nano-silver antibacterial material. Compared with the prior art, the method utilizes the full complexation of the sulfydryl and the nano silver, can realize the full dispersion and tight combination of the nano silver antibacterial agent in the material, and realizes the surface enrichment of the nano silver antibacterial agent. The invention also discloses application of the polyethylene wax-based nano silver antibacterial material in polyethylene injection products, the antibacterial material is used for injection molding of the polyethylene products, and the nano silver antibacterial agent is automatically enriched to the surfaces of the products depending on the difference of melt viscosities, so that the surface antibacterial effect of the polyethylene products is improved, and the dosage of the nano silver antibacterial agent is reduced.

Description

Preparation method of polyethylene wax-based nano-silver antibacterial material and application of polyethylene wax-based nano-silver antibacterial material in polyethylene injection molding products
Technical Field
The invention relates to the technical field of functional polymers, in particular to a preparation method of a polyethylene wax-based nano-silver antibacterial material and application of the material in polymer injection molding products.
Background
Polymer products have been widely used in various aspects of national life, but the polymer products do not have antibacterial performance. With the increasing pursuit of people for healthy life, antibacterial products become an important branch of the scientific development of materials at present. Antibacterial is a control measure to inhibit the growth of bacteria (microorganisms) and prevent the proliferation of bacteria. The antibacterial performance of the conventional antibacterial product is realized by doping functional antibacterial materials such as an antibacterial agent in the product, and the long-term sanitation of the product is kept by killing or inhibiting the propagation of bacteria on the surface of the material through surface contact. In China, along with the continuous increase of economy, the demand of antibacterial products is more and more extensive.
Currently, antibacterial agents are mainly classified into inorganic antibacterial agents and organic antibacterial agents, wherein nano-silver products are very superior in antibacterial performance and are one of the antibacterial agents with the best antibacterial efficiency and broad-spectrum antibacterial effect in recent years. At present, a large amount of nano-silver technology is adopted in plastic products to improve the antibacterial performance of polymer products. However, the nano silver antibacterial agent is relatively high in cost and belongs to a contact type antibacterial agent, so that how to reduce the dosage of the nano silver antibacterial agent while maintaining the antibacterial effect becomes a key problem that the nano silver antibacterial agent is popularized in plastic products at present.
Polyethylene resin is a polymer product widely used in general-purpose resin at present, and products thereof are very abundant and reach many corners of daily life. Under the situation that the global epidemic prevention form is more severe at present, the antibacterial performance of the product is improved, and the product has a very positive effect on guaranteeing healthy life. However, the conventional nano silver antibacterial agent is used in a large amount in the polyethylene resin, and a large amount of the nano silver antibacterial agent distributed in the resin does not substantially play an antibacterial role, and only the nano silver antibacterial agent on the surface can effectively play a bacteriostatic and bactericidal role. Therefore, how to realize the selective surface migration effect of the nano-silver antibacterial agent in the conventional process becomes a key point and a difficulty point of the research of polyethylene antibacterial products.
In view of the above, the present inventors have conducted extensive studies.
Disclosure of Invention
The invention aims to provide a preparation method of a polyethylene wax-based nano silver antibacterial material with high dispersibility and surface enrichment capacity.
The invention also aims to provide application of the polyethylene wax-based nano silver antibacterial material with high dispersibility and surface enrichment capacity in polyethylene injection molded products.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a polyethylene wax-based nano-silver antibacterial material is characterized by comprising the following steps: firstly, preparing sulfhydrylation polyethylene wax, then uniformly mixing the sulfhydrylation modified polyethylene wax and the nano-silver antibacterial agent to obtain the polyethylene wax-based nano-silver antibacterial material.
Further, the nano-silver antibacterial agent is nano-silver particles, and comprises nano-silver elementary substance particles and/or carrier-loaded nano-silver particles.
Further, the nano silver particles comprise carrier-loaded nano silver particles, and the carrier-loaded nano silver particles comprise Ag-CuO, Ag-ZnO, Ag-TiO and Ag-Al2O3At least one of (1).
Further, in the preparation of the sulfhydrylated polyethylene wax, the polyethylene wax is subjected to epoxidation modification, and then mercaptoethylamine is added into the polyethylene wax subjected to epoxidation modification to obtain the sulfhydrylated polyethylene wax.
Further, the mercapto-functionalized polyethylene wax has a molar ratio of mercapto groups to epoxy groups of from 0.2 to 0.73.
Further, in the polyethylene wax-based nano silver antibacterial material, the silver content is 10-40 wt%.
Further, the number average molecular weight of the polyethylene wax is 6000-15000.
Further, the basic structural formula of the polyethylene wax-based nano silver antibacterial material is as follows:
Figure BDA0002633202920000031
after the technical scheme is adopted, the preparation method of the polyethylene wax-based nano-silver antibacterial material has the following beneficial effects:
(1) through strong interaction (complexing action) between sulfydryl in the sulfhydrylation polyethylene wax and the nano-silver antibacterial agent, stable dispersion of the nano-silver antibacterial agent in the polyethylene wax is realized, the purposes of reducing agglomeration and improving the dispersibility of the nano-silver antibacterial agent are achieved, and uniform and stable dispersion of the nano-silver antibacterial agent in the material can be realized.
(2) The prepared polyethylene wax-based nano-silver antibacterial material reduces the dosage of the nano-silver antibacterial agent under the condition of not reducing the antibacterial effect, and can reduce the dosage by 15 to 28 percent under the general condition.
(3) The polyethylene wax is used as a base material, so that the antibacterial effect is achieved, the melt fluidity of the polyethylene resin can be partially adjusted, and the processing fluidity of the polyethylene and the composite material thereof is improved.
The utility model provides an application of polyethylene wax base nanometer silver antibacterial material in polyethylene injection moulding, polyethylene wax base nanometer silver antibacterial material is used for polyethylene injection moulding's injection moulding, polyethylene wax base nanometer silver antibacterial material and polyethylene resin melt-blending, then injection moulding.
Further, the polyethylene is high density polyethylene, and the melt index of the high density polyethylene is between 0.2 and 6.5 g/min.
After the technical scheme is adopted, the application of the polyethylene wax-based nano silver antibacterial material in polyethylene injection molding products has the following beneficial effects: in the injection molding process, the difference between the viscosity of the polyethylene-based nano-silver antibacterial material and the viscosity of the matrix resin melt is utilized to realize the effect of automatically enriching the nano-silver antibacterial agent to the surface of the product, so that the surface antibacterial effect of the polyethylene product is improved, and the dosage of the nano-silver antibacterial agent is reduced.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The invention relates to a polyethylene wax-based nano-silver antibacterial material, which has the following basic structural formula:
Figure BDA0002633202920000041
the polyethylene wax-based nano-silver antibacterial material is suitable for injection molding of polyethylene products, has high dispersibility and high stability, and after the polyethylene wax-based nano-silver antibacterial material is added into the polyethylene products, the nano-silver antibacterial agent is automatically enriched to the surfaces of the products in the injection molding process depending on the difference of melt viscosity, so that the surface antibacterial effect of the polyethylene products is improved, and the dosage of the nano-silver antibacterial agent is reduced.
Example 2
The invention relates to a preparation method of a polyethylene wax-based nano-silver antibacterial material (the structure is shown in example 1), which comprises the steps of firstly preparing sulfhydrylated polyethylene wax, then uniformly mixing the sulfhydrylated modified polyethylene wax with a nano-silver antibacterial agent, then fully complexing sulfhydryls and nano-silver to realize full dispersion and tight combination of the nano-silver antibacterial agent in functionalized (namely sulfhydrylated) polyethylene wax, and then carrying out molding treatment to obtain the polyethylene wax-based nano-silver antibacterial material, wherein the antibacterial material is granular, namely the antibacterial material is antibacterial master batch.
As a preferred embodiment, the nano-silver antibacterial agent is nano-silver particles. In the invention, the nano silver particles comprise nano silver elementary substance particles and/or carrier-loaded nano silver particles.
Further, the nano silver particles loaded on the carrier comprise Ag-CuO, Ag-ZnO, Ag-TiO and Ag-Al2O3At least one of (1).
As a preferred embodiment, the polyethylene wax used has a number average molecular weight of 6000-15000.
In a preferred embodiment, in the preparation of the thiolated polyethylene wax, the polyethylene wax is first subjected to epoxidation modification, and mercaptoethylamine is added to the epoxidized modified polyethylene wax to obtain the thiolated polyethylene wax.
Furthermore, in the polyethylene wax-based nano silver antibacterial material, the molar ratio of sulfydryl to epoxy groups in the sulfhydrylation polyethylene wax is 0.2-0.73.
As a preferred embodiment, the polyethylene wax-based nano silver antibacterial material is prepared from the following raw materials: sulfhydrylated polyethylene wax, an antioxidant and a nano-silver antibacterial agent.
Further, the antioxidant comprises antioxidant 1010 and/or antioxidant 168.
The preparation method of the polyethylene wax-based nano-silver antibacterial material has the following beneficial effects:
1. through strong interaction (complexing action) between sulfydryl in the sulfhydrylation polyethylene wax and the nano-silver antibacterial agent, stable dispersion of the nano-silver antibacterial agent in the polyethylene wax is realized, the purposes of reducing agglomeration and improving the dispersibility of the nano-silver antibacterial agent are achieved, and uniform and stable dispersion of the nano-silver antibacterial agent in the material can be realized.
2. The prepared polyethylene wax-based nano-silver antibacterial material reduces the dosage of the nano-silver antibacterial agent under the condition of not reducing the antibacterial effect, and can reduce the dosage by 15 to 28 percent under the general condition.
3. The polyethylene wax is used as a base material, so that the antibacterial effect is achieved, the melt fluidity of the polyethylene resin can be partially adjusted, and the processing fluidity of the polyethylene and the composite material thereof is improved.
Example 3
The invention relates to a preparation method of a polyethylene wax-based nano-silver antibacterial material, which comprises the following steps:
(1) epoxidation modification: fully melting polyethylene wax in a reaction kettle, controlling the temperature at 120-180 ℃, and then adding an initiator (0.2-0.8 wt%) and glycidyl methacrylate (1-15 wt%) for reaction to realize the epoxidation modification of the polyethylene wax;
(2) sulfhydrylation modification: adding mercaptoethylamine (2-10 wt%) into the epoxidized modified polyethylene wax melt to continue to react, thereby realizing the mercaptolation modification of the polyethylene wax;
(3) transferring the sulfhydrylation modified polyethylene wax melt obtained in the step (2) into a planetary stirrer, adding a nano-silver antibacterial agent (the silver content is 10-40 wt%), and mixing at a high speed to realize uniform and stable dispersion of the nano-silver antibacterial agent in the functionalized (namely sulfhydrylation) polyethylene wax to obtain a material melt;
(4) and (4) cooling and granulating the material melt obtained in the step (3) in the discharging process to obtain the polyethylene wax-nano silver antibacterial material.
The invention relates to a preparation method of a polyethylene wax-based nano-silver antibacterial material, which comprises the following specific reaction equation:
Figure BDA0002633202920000061
as a preferable embodiment, the epoxidation modification reaction time of the step (1) is 2h to 4h, and the sulfhydrylation modification reaction of the step (2) is 10h to 16 h.
As a preferable embodiment, the sulfhydrylated polyethylene wax is added into a stirrer, heated to a molten state, mixed with the nano-silver antibacterial agent, and stirred at a high speed (3000rpm) for 0.5 to 2 hours.
As a preferred embodiment, the initiator in step (1) is a free radical initiator, and mainly comprises one or more (two or more) of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Example 4
The invention relates to a preparation method of a polyethylene wax-based nano-silver antibacterial material, which specifically comprises the following steps:
10kg of polyethylene wax is added into a 20L reaction kettle, the temperature is controlled at 160 ℃, after the polyethylene wax is fully melted, 1.2kg of Glycidyl Methacrylate (GMA) and 0.5 wt% of initiator (di-tert-butyl peroxide) are added, and the reaction is carried out for 2 hours at constant temperature under the protection of nitrogen, wherein the grafting ratio reaches 2.3% (mol ratio). Then, 0.7kg of mercaptoethylamine was added to the reaction system, and the reaction was continued for 12 hours to prepare a mercaptolated polyethylene wax in which the molar ratio of mercapto group to epoxy group was 0.53. And washing the obtained reaction product with ethanol repeatedly, and purifying.
And then adding the sulfhydrylated polyethylene wax into a planetary stirring reactor, heating to a melting state (80-180 ℃), adding 2.3kg of nano-silver particles, mixing at a high speed (3000rpm) and stirring for 0.5-2h, then adding 1 wt% of antioxidant (antioxidant 1010 and antioxidant 168), discharging while hot, and preparing into a granular material, wherein the silver content in the polyethylene wax-based nano-silver antibacterial material reaches 14.2 wt%.
Example 5
The invention relates to a preparation method of an antibacterial polyethylene product prepared from a polyethylene wax-based nano silver antibacterial material and polyethylene, which comprises the following steps: the polyethylene wax-based nano silver antibacterial material of the above example 1, 2, 3 or 4 and polyethylene resin are melt-blended and then injection-molded.
The polyethylene wax-based nano silver antibacterial material can be directly and fully mixed with the polyethylene resin particles and then directly subjected to injection molding.
As a preferred embodiment, the polyethylene resin includes at least one of High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE) and Low Density Polyethylene (LDPE).
The polyethylene wax-based nano silver antibacterial material provided by the invention is suitable for processing polyethylene matrix resin and various composite material products of polyethylene resin.
As a preferred embodiment, the polyethylene resin is a high density polyethylene having a melt index of from 0.2 to 6.5 g/min.
As a preferable embodiment, the injection molding temperature is 160-220 ℃, the injection molding pressure is adjusted according to the product properties and the flow channel design, and high-speed injection molding is recommended to be adopted, so that the enrichment effect of the antibacterial material on the surface of the injection molded product is favorably realized.
Example 6
The invention relates to a preparation method of an antibacterial polyethylene product prepared from a polyethylene wax-based nano silver antibacterial material and polyethylene, which comprises the following steps:
(1)10kg of high density polyethylene (melt index of 0.33g/min), 0.2kg of polyethylene wax-based nano silver antibacterial material (prepared in example 4 above) was added, melt-blended on a twin-screw extruder, cooled, granulated, and sufficiently dried.
(2) And (3) ageing the fused and blended particles for 24 hours, and then directly performing injection molding at the injection molding temperature of 210 ℃ to obtain the antibacterial polyethylene product.
The basic mechanical properties of the antimicrobial polyethylene article of this example are shown in table 1:
TABLE 1 mechanical Properties of antimicrobial polyethylene products
Figure BDA0002633202920000081
Figure BDA0002633202920000091
The basic antimicrobial properties of the antimicrobial polyethylene article of this example are shown in table 2:
TABLE 2 antimicrobial Properties of antimicrobial polyethylene products
Figure BDA0002633202920000092
In addition, characterization of the enrichment property of the surface of the nano-silver particles:
silver content in 0.2mm surface layer/silver content of product as a whole 3.65
Wherein the silver content is measured by atomic absorption spectroscopy, and the average of 5 samples is obtained.
Example 7
The invention relates to a preparation method of an antibacterial polyethylene product prepared from a polyethylene wax-based nano silver antibacterial material and polyethylene, which comprises the following steps:
(1)10kg of high density polyethylene (melt index 0.33g/min) was added with 0.2kg of polyethylene wax-based antibacterial material (prepared in example 4 above) and mixed in a high speed mixer for 10 min.
(2) The blended particles were directly injection molded at a temperature of 210 ℃.
The basic mechanical properties of the antimicrobial polyethylene article of this example are shown in table 3:
TABLE 3 mechanical Properties of the antimicrobial polyethylene products
Figure BDA0002633202920000101
The basic antimicrobial properties of the antimicrobial polyethylene articles of this example are shown in table 4:
TABLE 4 antimicrobial Properties of antimicrobial polyethylene products
Figure BDA0002633202920000102
In addition, characterization of the enrichment property of the surface of the nano-silver particles:
the silver content in the 0.2mm surface layer/silver content of the product as a whole was 3.02.
Wherein the silver content is measured by atomic absorption spectroscopy, and the average of 5 samples is obtained.
Example 8
High-density polyethylene with different melt indexes is used as a matrix to prepare the antibacterial polyethylene product.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to improve the antibacterial performance of a polyethylene product, and high-density polyethylenes with different melt indexes are used as a substrate, which is specifically described as follows:
(1)10kg of high density polyethylene, 0.2kg of polyethylene wax-based antibacterial material was added, melt-blended on a twin-screw extruder, cooled, granulated, and sufficiently dried.
(2) After aging for 24 hours, the melt blended particles are directly subjected to injection molding at the injection molding temperature of 210 ℃.
In order to further increase the influence of the melt viscosity of the high-density polyethylene matrix on the surface migration of the antibacterial material, a plurality of antibacterial polyethylenes were prepared by the above method, and the specific properties are shown in table 5:
TABLE 5 influence of matrix melt viscosity on the surface enrichment behavior of antimicrobial materials
Figure BDA0002633202920000111
Therefore, the nano-silver antibacterial agent master batch with low melt viscosity is adopted, and selective enrichment to the surface of a product part is realized in the injection molding process. The greater the melt viscosity (lower melt index) of the substrate, the more pronounced the surface enrichment phenomenon. Therefore, the surface antibacterial performance of the product can be effectively improved through the surface enrichment effect of the nano silver particles.
Example 9
Preparing the antibacterial polyethylene product with different antibacterial material contents.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to improve the antibacterial performance of the polyethylene product, and different antibacterial materials are added in different amounts, which are specifically described as follows:
(1)10kg of high density polyethylene (melt index of 0.33), adding polyethylene wax-based antibacterial materials with different contents, melting and blending on a double-screw extruder, cooling and granulating, and fully drying.
(2) After aging for 24 hours, the melt blended particles are directly subjected to injection molding at the injection molding temperature of 210 ℃.
Figure BDA0002633202920000121
Therefore, in the present invention, when the amount of the antibacterial material exceeds 1%, an excellent antibacterial rate against Escherichia coli can be achieved.
The above embodiments are not intended to limit the methods and applications of the products of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.

Claims (10)

1. A preparation method of a polyethylene wax-based nano-silver antibacterial material is characterized by comprising the following steps: firstly, preparing sulfhydrylation polyethylene wax, then uniformly mixing the sulfhydrylation modified polyethylene wax and the nano-silver antibacterial agent to obtain the polyethylene wax-based nano-silver antibacterial material.
2. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, wherein the method comprises the following steps: the nano silver antibacterial agent is nano silver particles, and comprises nano silver simple substance particles and/or carrier-loaded nano silver particles.
3. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 2, wherein the method comprises the following steps: the nano silver particles comprise nano silver particles loaded on a carrier, and the nano silver particles loaded on the carrier comprise Ag-CuO, Ag-ZnO, Ag-TiO and Ag-Al2O3At least one of (1).
4. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, wherein the method comprises the following steps: in the preparation of the sulfhydrylated polyethylene wax, the polyethylene wax is firstly subjected to epoxidation modification, and then mercaptoethylamine is added into the polyethylene wax subjected to epoxidation modification to obtain the sulfhydrylated polyethylene wax.
5. The method for preparing a polyethylene wax-based nano-silver antibacterial material according to claim 1 or 4, wherein: the mercapto polyethylene wax has a mercapto to epoxy molar ratio of from 0.2 to 0.73.
6. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, wherein the method comprises the following steps: in the polyethylene wax-based nano silver antibacterial material, the silver content is 10-40 wt%.
7. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, wherein the method comprises the following steps: the number average molecular weight of the polyethylene wax is 6000-15000.
8. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, wherein the basic structural formula of the polyethylene wax-based nano-silver antibacterial material is as follows:
Figure FDA0002633202910000021
9. the use of the polyethylene wax-based nano silver antibacterial material as claimed in claim 1 in polyethylene injection-molded articles, wherein: the polyethylene wax-based nano silver antibacterial material is used for injection molding of polyethylene products, and is subjected to melt blending with polyethylene resin and then injection molding.
10. The use of the polyethylene-based nanosilver antibacterial material as claimed in claim 9 in polyethylene injection molded articles, wherein: the polyethylene resin is high-density polyethylene, and the melt index of the high-density polyethylene is 0.2-6.5 g/min.
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