CN112063065B - Preparation method of polyethylene wax-based nano silver antibacterial material and application of material in polyethylene injection molding products - Google Patents

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

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CN112063065B
CN112063065B CN202010817393.0A CN202010817393A CN112063065B CN 112063065 B CN112063065 B CN 112063065B CN 202010817393 A CN202010817393 A CN 202010817393A CN 112063065 B CN112063065 B CN 112063065B
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nano silver
polyethylene wax
polyethylene
silver antibacterial
antibacterial material
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CN112063065A (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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Xiamen Make Security Technology Co Ltd
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    • C08K3/00Use of inorganic substances as compounding ingredients
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2003/0806Silver
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE
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    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

Abstract

The invention discloses a preparation method of a polyethylene wax-based nano silver antibacterial material, which comprises the steps of firstly preparing a sulfhydrylation polymer, then uniformly mixing the sulfhydrylation modified polymer and a nano silver antibacterial agent, and finally obtaining the antibacterial material. Compared with the prior art, the invention utilizes the sulfydryl and the nano silver to fully complex, can realize the full dispersion and tight combination of the nano silver antibacterial agent in the material, and realizes the surface enrichment effect of the nano silver antibacterial agent. The invention also discloses an application of the polyethylene wax-based nano silver antibacterial material in polyethylene injection molding products, the antibacterial material is used for the injection molding of polyethylene products, and the nano silver antibacterial agent is automatically enriched to the surface of the products by virtue of the difference of melt viscosity, so that the surface antibacterial effect of the polyethylene products is improved, and the consumption of the nano silver antibacterial agent is reduced.

Description

Preparation method of polyethylene wax-based nano silver antibacterial material and application of 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 the life of the national world, but the polymer products themselves do not have antibacterial properties. With the pursuit of healthy life, antibacterial products have become an important branch of the current development of material science. Antibacterial is a control measure that inhibits the growth of bacteria (microorganisms) and prevents the proliferation of bacteria. The antibacterial performance of the conventional antibacterial product is mainly realized by doping functional antibacterial materials such as antibacterial agents and the like into the product, and bacteria on the surface of the material are killed or inhibited from propagating through surface contact, so that the long-term sanitation of the product is maintained. In China, along with the continuous increase of economy, the demand for antibacterial products is becoming wider and wider.
At present, the antibacterial agents are mainly classified into inorganic antibacterial agents and organic antibacterial agents, wherein the antibacterial performance of nano silver products is very excellent, and the nano silver products are one of 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 has high cost and belongs to a contact antibacterial agent, so that the use amount of the nano silver antibacterial agent is reduced while the antibacterial effect is maintained, and the nano silver antibacterial agent becomes a key problem in popularization in plastic products at present.
Polyethylene resins, which are widely used polymer products among general-purpose resins at present, are very abundant in products, and have reached many corners of daily life. Under the situation that the global epidemic prevention mode is becoming 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 large in dosage in polyethylene resin, and a large amount of nano silver antibacterial agent distributed in the resin does not play a role in antibacterial effect, and only the nano silver antibacterial agent on the surface can play a role in antibacterial and sterilizing effectively. 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 difficult point of research on polyethylene antibacterial products.
In view of this, the present inventors have conducted intensive 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 capability.
The invention further aims to provide an application of the polyethylene wax-based nano silver antibacterial material with high dispersibility and surface enrichment capability in polyethylene injection molding products.
In order to achieve the above 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 of: firstly preparing sulfhydrylation polyethylene wax, then uniformly mixing the sulfhydrylation modified polyethylene wax and the nano silver antibacterial agent, and finally obtaining the polyethylene wax-based nano silver antibacterial material.
Further, the nano silver antibacterial agent is nano silver particles, and comprises nano silver simple substance particles and/or nano silver particles loaded by a carrier.
Further, the nano silver particles comprise nano silver particles loaded by a carrier, and the nano silver particles loaded by the carrier comprise Ag-CuO, ag-ZnO, ag-TiO and Ag-Al 2 O 3 At least one of them.
Further, in the preparation of the sulfhydrylated polyethylene wax, the polyethylene wax is subjected to epoxidation modification, and then the sulfhydryl ethylamine is added into the polyethylene wax subjected to epoxidation modification to obtain the sulfhydrylated polyethylene wax.
Further, the molar ratio of mercapto groups to epoxy groups in the mercapto polyethylene wax is 0.2 to 0.73.
Further, in the polyethylene wax-based nano silver antibacterial material, the silver content is 10-40 wt%.
Further, the polyethylene wax has a number average molecular weight of 6000 to 15000.
Further, the basic structural formula of the polyethylene wax-based nano silver antibacterial material is as follows:
after the technical scheme is adopted, the preparation method of the polyethylene wax-based nano silver antibacterial material has the following beneficial effects:
(1) The stable dispersion of the nano silver antibacterial agent in the polyethylene wax is realized through the strong interaction (complexation) between the mercapto group in the mercapto polyethylene wax and the nano silver antibacterial agent, the purposes of reducing agglomeration and improving the dispersibility are achieved, and the 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 15-28% 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 regulated, and the processing fluidity of the polyethylene and the composite material thereof is improved.
The application of the polyethylene wax-based nano silver antibacterial material in polyethylene injection molding products is that the polyethylene wax-based nano silver antibacterial material is used for injection molding of the polyethylene products, and the polyethylene wax-based nano silver antibacterial material is melt blended with polyethylene resin and then injection molded.
Further, the polyethylene is high-density polyethylene, and the melt index of the high-density polyethylene is between 0.2 and 6.5g/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 effect of automatically enriching the nano silver antibacterial agent to the surface of the product is realized by utilizing the difference of the melt viscosities of the polyethylene wax-based nano silver antibacterial material and the matrix resin, 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 scheme of the invention, the invention is explained in detail by specific examples.
Example 1
The invention relates to a polyethylene wax-based nano silver antibacterial material, which has the following basic structural formula:
the polyethylene wax-based nano silver antibacterial material is suitable for injection molding of polyethylene products, has high dispersibility and high stability, realizes automatic enrichment of nano silver antibacterial agent to the surface of the product by means of the difference of melt viscosity in the injection molding process after the polyethylene wax-based nano silver antibacterial material is added into the polyethylene products, improves the surface antibacterial effect of the polyethylene products, and reduces the dosage of the nano silver antibacterial agent.
Example 2
The invention relates to a preparation method of a polyethylene wax-based nano silver antibacterial material (with a structure as in an embodiment 1), which comprises the steps of firstly preparing sulfhydrylated polyethylene wax, then uniformly mixing sulfhydrylated modified polyethylene wax and nano silver antibacterial agent, then fully complexing by utilizing sulfhydryl and nano silver to realize the full dispersion and tight combination of the nano silver antibacterial agent in the functionalized (i.e. sulfhydrylated) polyethylene wax, and then obtaining the polyethylene wax-based nano silver antibacterial material after molding treatment, wherein the antibacterial material is in particular in a particle shape, i.e. 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 simple substance particles and/or nano silver particles loaded by a carrier.
Further, the nano silver particles supported by the carrier comprise Ag-CuO, ag-ZnO, ag-TiO and Ag-Al 2 O 3 At least one of them.
As a preferred embodiment, the polyethylene wax used has a number average molecular weight of 6000 to 15000.
In a preferred embodiment, in preparing the sulfhydrylated polyethylene wax, the polyethylene wax is subjected to epoxidation modification, and then the mercaptoethylamine is added into the polyethylene wax subjected to epoxidation modification to obtain the sulfhydrylated polyethylene wax.
Further, in the polyethylene wax base nano silver antibacterial material, the molar ratio of mercapto group to epoxy group in the mercapto polyethylene wax is 0.2-0.73.
As a preferred embodiment, the polyethylene wax base nano silver antibacterial material is prepared from the following raw materials: sulfhydrylated polyethylene wax, an antioxidant and a nano silver antibacterial agent.
Further, antioxidants include antioxidant 1010 and/or antioxidant 168.
The preparation method of the polyethylene wax-based nano silver antibacterial material has the following beneficial effects:
1. the stable dispersion of the nano silver antibacterial agent in the polyethylene wax is realized through the strong interaction (complexation) between the mercapto group in the mercapto polyethylene wax and the nano silver antibacterial agent, the purposes of reducing agglomeration and improving the dispersibility are achieved, and the 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 15-28% 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 regulated, 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) And (3) epoxidation modification: fully melting polyethylene wax in a reaction kettle, controlling the temperature to be 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) Thiol modification: adding mercaptoethylamine (2-10wt%) into the epoxy modified polyethylene wax melt for continuous reaction to realize mercapto modification of the polyethylene wax;
(3) Transferring the mercapto-modified polyethylene wax melt 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 (i.e. mercapto) polyethylene wax and obtain a material melt;
(4) And (3) cooling and granulating the material melt in the step (3) in the discharging process to obtain the polyethylene wax-based 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:
as a preferred embodiment, the epoxidation modification reaction time of the step (1) is 2 to 4 hours, and the mercapto modification reaction of the step (2) is 10 to 16 hours.
As a preferred embodiment, the above sulfhydrylated polyethylene wax is added into a stirrer, heated to a molten state, mixed with the nano silver antibacterial agent, and mixed for 0.5-2 hours under the condition of high-speed stirring (3000 rpm).
As a preferred embodiment, the initiator in step (1) is a radical initiator mainly comprising one or more (two or more) of benzoyl peroxide, lauroyl peroxide, di-t-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 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 0.5wt% of initiator (di-tert-butyl peroxide) are added, and the reaction is carried out for 2 hours under the protection of nitrogen, so that the grafting rate 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 mercapto polyethylene wax in which the molar ratio of mercapto groups to epoxy groups was 0.53. The obtained reaction product was repeatedly washed with ethanol and purified.
Then adding the sulfhydrylation polyethylene wax into a planetary stirring reactor, heating to a molten state (80-180 ℃), adding 2.3kg of nano silver particles, stirring at a high speed (3000 rpm) for 0.5-2h, then adding 1wt% of antioxidant (antioxidant 1010 and antioxidant 168), discharging while the mixture is hot, and preparing a granular material, wherein the silver content in the polyethylene wax-based nano silver antibacterial material reaches 14.2wt%.
Example 5
The invention relates to a preparation method of an antibacterial polyethylene product by using 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 was melt-blended with polyethylene resin and then injection-molded.
The invention can also be directly injection molded after fully mixing the polyethylene wax base nano silver antibacterial material with polyethylene resin particles.
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 applicable to processing of 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 0.2 to 6.5g/min.
As a preferred implementation mode, the temperature of the injection molding is 160-220 ℃, the injection molding pressure is adjusted according to the product property and the runner design, and high-speed injection molding is suggested to be adopted, so that the enrichment effect of the antibacterial material on the surface of an injection molded product is facilitated.
Example 6
The invention relates to a preparation method of an antibacterial polyethylene product by using a polyethylene wax-based nano silver antibacterial material and polyethylene, which comprises the following steps:
(1) 10kg of high density polyethylene (melt index 0.33 g/min) was added with 0.2kg of polyethylene wax-based nano silver antibacterial material (prepared in example 4 above), melt blended on a twin screw extruder, cooled to pelletize, and sufficiently dried.
(2) And (3) after the particles are melted and blended, aging for 24 hours, directly performing injection molding, wherein the injection molding temperature is 210 ℃, and obtaining the antibacterial polyethylene product.
The basic mechanical properties of the antimicrobial polyethylene product of this example are shown in table 1:
TABLE 1 mechanical Properties of antibacterial polyethylene products
The basic antimicrobial properties of the antimicrobial polyethylene articles of this example are shown in table 2:
table 2 antimicrobial properties of antimicrobial polyethylene products
Furthermore, characterization of the surface enrichment properties of the nano silver particles:
silver content in 0.2mm surface layer/silver content of the product overall = 3.65
The silver content was measured by atomic absorption spectrometry, and an average value of 5 samples was taken.
Example 7
The invention relates to a preparation method of an antibacterial polyethylene product by using a polyethylene wax-based nano silver antibacterial material and polyethylene, which comprises the following steps:
(1) 10kg of high-density polyethylene (melt index 0.33 g/min), 0.2kg of polyethylene wax-based antibacterial material (prepared as described in example 4 above) were added and mixed in a high-speed mixer for 10min.
(2) The blended particles are directly injection molded, and the injection molding temperature is 210 ℃.
The basic mechanical properties of the antimicrobial polyethylene product of this example are shown in table 3:
TABLE 3 mechanical Properties of antibacterial polyethylene products
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
Furthermore, characterization of the surface enrichment properties of the nano silver particles:
silver content in 0.2mm surface layer/silver content of the product overall = 3.02.
The silver content was measured by atomic absorption spectrometry, and an average value of 5 samples was taken.
Example 8
The antibacterial polyethylene products are prepared by taking high-density polyethylene with different melt indexes as a matrix.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to achieve the effect of improving the antibacterial performance of polyethylene products, and high-density polyethylene with different melt indexes is used as a matrix, which is specifically described as follows:
(1) 10kg of high-density polyethylene, 0.2kg of polyethylene wax-based antibacterial material are added, melt-blended on a twin-screw extruder, cooled and granulated, and sufficiently dried.
(2) And (3) after the melt blending, aging for 24 hours, directly performing injection molding, wherein the injection molding temperature is 210 ℃.
To further compare the effect of melt viscosity of high density polyethylene matrix on surface mobility of antimicrobial materials, various antimicrobial polyethylenes were prepared using the method described above, the specific properties of which are shown in table 5:
TABLE 5 influence of the melt viscosity of the matrix on the surface enrichment properties of antibacterial materials
It can be seen that the use of nanosilver antimicrobial masterbatches with low melt viscosity allows for selective enrichment of the product surface during the injection process. The higher the melt viscosity of the matrix (lower the melt index), the more pronounced the surface enrichment phenomenon. Therefore, the surface antibacterial property of the product can be effectively improved through the surface enrichment effect of the nano silver particles.
Example 9
Different antibacterial material contents are used for preparing antibacterial polyethylene products.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to achieve the effect of improving the antibacterial performance of polyethylene products, and different addition amounts of the antibacterial material are adopted, which is specifically described as follows:
(1) 10kg of high-density polyethylene (melt index of 0.33), polyethylene wax-based antibacterial materials with different contents were added, melt-blended on a twin-screw extruder, cooled and granulated, and sufficiently dried.
(2) And (3) after the melt blending, aging for 24 hours, directly performing injection molding, wherein the injection molding temperature is 210 ℃.
Therefore, in the present invention, when the amount of the antibacterial material exceeds 1%, an excellent antibacterial efficiency against E.coli can be achieved.
The above embodiments are not intended to limit the method and application of the product of the present invention, and any suitable changes or modifications made by those skilled in the art should be construed as not departing from the scope of the invention.

Claims (6)

1. A preparation method of a polyethylene wax-based nano silver antibacterial material is characterized by comprising the following steps of: firstly preparing sulfhydrylation polyethylene wax, wherein the number average molecular weight of the polyethylene wax is 6000-15000, in the preparation of the sulfhydrylation polyethylene wax, firstly, performing epoxidation modification on the polyethylene wax, and then adding sulfhydryl ethylamine into the polyethylene wax subjected to epoxidation modification to obtain the sulfhydrylation polyethylene wax;
uniformly mixing the sulfhydrylation modified polyethylene wax and the nano silver antibacterial agent to obtain the polyethylene wax-based nano silver antibacterial material;
the reaction equation of the preparation process of the polyethylene wax-based nano silver antibacterial material is as follows:
the polyethylene wax-based nano silver antibacterial material is used for injection molding of polyethylene products, and is melt blended with polyethylene resin and then injection molded.
2. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, which is characterized by comprising the following steps: the nano silver antibacterial agent is nano silver particles, and comprises nano silver simple substance particles and/or nano silver particles loaded by a carrier.
3. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 2, which is characterized by comprising the following steps: the nano silver particles comprise nano silver particles loaded by a carrier, and the nano silver particles loaded by the carrier comprise Ag-CuO, ag-ZnO, ag-TiO and Ag-Al 2 O 3 At least one of them.
4. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, which is characterized by comprising the following steps: the molar ratio of mercapto groups to epoxy groups in the mercapto polyethylene wax is 0.2-0.73.
5. The method for preparing the polyethylene wax-based nano-silver antibacterial material according to claim 1, which is characterized by comprising the following steps: the silver content in the polyethylene wax-based nano silver antibacterial material is 10-40 wt%.
6. The use of the polyethylene wax-based nano-silver antibacterial material according to claim 1 in polyethylene injection-molded articles, wherein: the polyethylene resin is high-density polyethylene, and the melt index of the high-density polyethylene is 0.2-6.5g/min.
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