CN112094431A - Preparation method of polypropylene wax-based nano-silver antibacterial material and application of material in polypropylene injection-molded products - Google Patents
Preparation method of polypropylene wax-based nano-silver antibacterial material and application of material in polypropylene injection-molded products Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 157
- -1 polypropylene Polymers 0.000 title claims abstract description 157
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 157
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 42
- 238000001746 injection moulding Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 5
- 229960003151 mercaptamine Drugs 0.000 claims description 5
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 4
- 229910017933 Ag—Al2O3 Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 47
- 230000000845 anti-microbial effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
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- 239000002344 surface layer Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a preparation method of a polypropylene 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 an application of the polypropylene wax-based nano silver antibacterial material in polypropylene injection molding products, the antibacterial material is used for injection molding of the polypropylene 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 polypropylene products is improved, and the dosage of the nano silver antibacterial agent is reduced.
Description
Technical Field
The invention relates to the technical field of functional polymers, in particular to a preparation method of a polypropylene 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.
The polypropylene resin is a polymer product widely used in general-purpose resin at present, and products of the polypropylene resin are rich 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 polypropylene 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 the polypropylene antibacterial product.
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 polypropylene wax-based nano silver antibacterial material with high dispersibility and surface enrichment capacity.
The invention also aims to provide the application of the polypropylene wax-based nano silver antibacterial material with high dispersibility and surface enrichment capacity in polypropylene injection-molded products.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a polypropylene wax-based nano-silver antibacterial material comprises the steps of preparing sulfhydrylation polypropylene wax, and then uniformly mixing sulfhydrylation modified polypropylene wax and a nano-silver antibacterial agent to obtain the polypropylene 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 polypropylene wax, the polypropylene wax is subjected to epoxidation modification, and then mercaptoethylamine is added into the polypropylene wax subjected to epoxidation modification to obtain the sulfhydrylated polypropylene wax.
Further, the mercapto-modified polypropylene wax has a mercapto group to epoxy group molar ratio of 0.2 to 0.9.
Further, in the polypropylene wax-based nano silver antibacterial material, the silver content is 10-35 wt%.
Further, the number average molecular weight of the polypropylene wax is 8000-.
Further, the polypropylene wax-based nano silver antibacterial material has a basic structural formula as follows:
after the technical scheme is adopted, the preparation method of the polypropylene wax-based nano-silver antibacterial material has the following beneficial effects:
(1) the stable dispersion of the nano-silver antibacterial agent in the polypropylene wax is realized through the strong interaction (complexation) between the sulfydryl in the sulfhydrylation polypropylene wax and the nano-silver antibacterial agent, so that the aims of reducing agglomeration and improving the dispersibility of the nano-silver antibacterial agent are fulfilled, and the uniform and stable dispersion of the nano-silver antibacterial agent in the material can be realized.
(2) The prepared polypropylene wax-based nano-silver antibacterial material reduces the dosage of a nano-silver antibacterial agent under the condition of not reducing the antibacterial effect, and can reduce the dosage by 10 to 23 percent under the general condition.
(3) The polypropylene wax is adopted as the base material, not only has antibacterial effect, but also can partially adjust the melt fluidity of the polypropylene and improve the processing fluidity of the polypropylene and the composite material thereof
The polypropylene wax-based nano silver antibacterial material is used for injection molding of polypropylene products, and is fused and blended with polypropylene resin and then injection molded.
Further, the polypropylene resin has a melt index of 1.2 to 5.6 g/min.
After the technical scheme is adopted, the application of the polypropylene wax-based nano silver antibacterial material in polypropylene injection-molded products has the following beneficial effects: in the injection molding process, the difference between the viscosities of the polypropylene wax-based nano-silver antibacterial material and the matrix resin melt is utilized to realize the function of automatically enriching the nano-silver antibacterial agent to the surface of the product, thereby not only improving the surface antibacterial effect of the polypropylene product, but also reducing the dosage of the nano-silver antibacterial agent.
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 polypropylene wax-based nano silver antibacterial material, which has a basic structural formula as follows:
the polypropylene wax-based nano-silver antibacterial material is suitable for injection molding of polypropylene products, has high dispersibility and high stability, and after the polypropylene wax-based nano-silver antibacterial material is added into the polypropylene 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 polypropylene 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 polypropylene wax-based nano silver antibacterial material (the structure is as in example 1). This preparation method comprises the steps of firstly preparing sulfhydrylation polypropylene wax, then uniformly mixing sulfhydrylation modified polypropylene wax and a nano silver antibacterial agent, then fully complexing sulfhydryl and nano silver to realize full dispersion and tight combination of the nano silver antibacterial agent in functionalized (namely sulfhydrylation) polypropylene wax, and then carrying out molding treatment to obtain the polypropylene 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 polypropylene wax used has a number average molecular weight of 8000-.
In a preferred embodiment, in the preparation of the thiolated polypropylene wax, the polypropylene wax is subjected to epoxidation modification, and mercaptoethylamine is added to the epoxidation-modified polypropylene wax to obtain the thiolated polypropylene wax.
Furthermore, in the polypropylene wax-based nano silver antibacterial material, the mole ratio of sulfydryl to epoxy group in the sulfhydrylation polypropylene wax is 0.2-0.9.
As a preferred embodiment, the polypropylene wax-based nano silver antibacterial material is prepared from the following raw materials: sulfhydrylated polypropylene wax, an antioxidant and a nano-silver antibacterial agent.
Further, the antioxidant comprises antioxidant 1010 and/or antioxidant 168.
The preparation method of the polypropylene wax-based nano-silver antibacterial material has the following beneficial effects:
1. the stable dispersion of the nano-silver antibacterial agent in the polypropylene wax is realized through the strong interaction (complexation) between the sulfydryl in the sulfhydrylation polypropylene wax and the nano-silver antibacterial agent, so that the aims of reducing agglomeration and improving the dispersibility of the nano-silver antibacterial agent are fulfilled, and the uniform and stable dispersion of the nano-silver antibacterial agent in the material can be realized.
2. The prepared polypropylene wax-based nano-silver antibacterial material reduces the dosage of a nano-silver antibacterial agent under the condition of not reducing the antibacterial effect, and can reduce the dosage by 10 to 23 percent under the general condition.
3. The polypropylene wax is used as a base material, so that the antibacterial effect is achieved, the melt fluidity of the polypropylene resin can be partially adjusted, and the processing fluidity of the polypropylene and the composite material thereof is improved.
Example 3
The invention relates to a preparation method of a polypropylene wax-based nano silver antibacterial material, which comprises the following steps:
(1) epoxidation modification: fully melting polypropylene wax in a reaction kettle, controlling the temperature at 170-210 ℃, 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 polypropylene wax;
(2) sulfhydrylation modification: adding mercaptoethylamine (2-10 wt%) into the epoxidized modified polypropylene wax melt to continue to react to realize the sulfhydrylation modification of the polypropylene wax;
(3) transferring the sulfhydrylation modified polypropylene wax melt obtained in the step (2) into a planetary stirrer, adding a nano-silver antibacterial agent (the silver content is 10-30 wt%), and mixing at a high speed to realize uniform and stable dispersion of the nano-silver antibacterial agent in the functionalized (namely sulfhydrylation) polypropylene 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 polypropylene wax-based nano silver antibacterial material.
The invention relates to a preparation method of a polypropylene wax-based nano silver antibacterial material, which comprises the following specific reaction equation:
as a preferable embodiment, the epoxidation modification reaction time of the step (1) is 2h-4h, and the sulfhydrylation modification reaction of the step (2) is 10h-16 h.
As a preferable embodiment, the sulfhydrylated polypropylene 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 polypropylene wax-based nano silver antibacterial material, which specifically comprises the following steps:
10kg of polypropylene wax is added into a 20L reaction kettle, the temperature is controlled at 180 ℃, after the polypropylene wax is fully melted, 1.2kg of Glycidyl Methacrylate (GMA) and 0.5 wt% of initiator (di-tert-butyl peroxide) are added, the reaction is carried out for 2 hours under the condition of nitrogen protection, and the grafting rate reaches 4.3% (mol ratio). Then, 0.7kg of mercaptoethylamine was added to the reaction system, and the reaction was continued for 12 hours to prepare a mercaptozed polypropylene wax in which the molar ratio of mercapto group to epoxy group was 0.42, and the resulting reaction product was repeatedly washed with ethanol and purified.
And then adding the sulfhydrylation polypropylene wax into a planetary stirring reactor, heating to a melting state (80-180 ℃), adding 3.1kg of nano-silver particles, mixing and stirring at a high speed for 0.5-2h, then adding 1 wt% of antioxidant (antioxidant 1010 and antioxidant 168), discharging while the mixture is hot, and preparing into a granular master batch, wherein the silver content in the polypropylene wax-based nano-silver antibacterial material reaches 18.7 wt%.
Example 5
The invention relates to a preparation method of a polypropylene wax-based nano silver antibacterial material and an antibacterial polypropylene product prepared from polypropylene, which comprises the following steps: the polypropylene wax-based nano silver antibacterial material of the embodiment 1, 2, 3 or 4 and the polypropylene resin are subjected to melt blending and then injection molding.
It should be noted that, the invention can also directly mix the polypropylene wax-based nano silver antibacterial material with the polypropylene resin particles, and then directly perform injection molding.
The polypropylene wax-based nano silver antibacterial material provided by the invention is suitable for processing polypropylene matrix resin and various composite material products of the polypropylene resin.
As a preferred embodiment, the polypropylene resin has a melt index of 1.2 to 5.6 g/min.
As a preferable embodiment, the injection molding temperature is 190-230 ℃, 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 a polypropylene wax-based nano silver antibacterial material and an antibacterial polypropylene product prepared from polypropylene, which comprises the following steps:
(1)10kg of polypropylene (melt index of 1.6g/min), 0.2kg of a polypropylene wax-based antibacterial material (prepared in example 4 above) was added, melt-blended on a twin-screw extruder, cooled, granulated, and sufficiently dried.
(2) And (3) aging 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 polypropylene product.
The basic mechanical properties of the antimicrobial polypropylene article of this example are shown in table 1:
TABLE 1 mechanical Properties of antimicrobial Polypropylene products
The basic antimicrobial properties of the antimicrobial polypropylene articles of this example are shown in table 2:
TABLE 2 antimicrobial Properties of antimicrobial Polypropylene products
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 3.25.
Wherein the silver content is measured by atomic absorption spectroscopy, taking the average of 5 samples.
Example 7
The invention relates to a preparation method of a polypropylene wax-based nano silver antibacterial material and an antibacterial polypropylene product prepared from polypropylene, which comprises the following steps:
(1)10kg of polypropylene (melt index 1.6g/min), 0.2kg of a polypropylene wax-based antibacterial material was added and mixed in a high-speed mixer for 10 min.
(2) And (3) directly performing injection molding on the blended particles at the injection molding temperature of 210 ℃ to obtain the antibacterial polypropylene product.
The basic mechanical properties of the antimicrobial polypropylene article of this example are shown in table 3:
TABLE 3 mechanical Properties of the antimicrobial Polypropylene product
The basic antimicrobial properties of the antimicrobial polypropylene articles of this example are shown in table 4:
TABLE 4 antimicrobial Properties of antimicrobial Polypropylene products
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 2.79.
Wherein the silver content is measured by atomic absorption spectroscopy, taking the average of 5 samples.
Example 8
Polypropylene with different melt indexes is used as a matrix to prepare the antibacterial polypropylene product.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to improve the antibacterial performance of a polypropylene product, and polypropylenes with different melt indexes are used as a substrate, and are specifically described as follows:
(1)10kg of polypropylene, 0.2kg of polypropylene wax-based antibacterial material is added, and the mixture is melted and blended on a double-screw extruder, cooled, granulated and fully dried.
(2) After aging for 24 hours, the melt blended particles are directly subjected to injection molding at the injection molding temperature of 210 ℃.
To further compare the effect of the melt viscosity of the polypropylene matrix on the surface mobility of the antimicrobial material, a number of antimicrobial polypropylenes were prepared using the above method, with specific properties as shown in table 5:
TABLE 5 influence of matrix melt viscosity on the surface enrichment behavior of antimicrobial materials
It should be noted that, in samples 1-4, the difference between the silver contents of the effective antibacterial component nano silver is not great, but when the antibacterial material developed by the present application is adopted, because the melt indexes of the antibacterial material are greatly different, depending on the difference of the melt viscosities in the injection molding process, the enrichment degree of the nano silver antibacterial material on the surface of the product is improved, and further, the antibacterial effect of the antibacterial material is improved.
Example 9
Preparing the antibacterial polypropylene product with different antibacterial master batch contents.
In this embodiment, the antibacterial material prepared in embodiment 4 is used as an additive to improve the antibacterial performance of the polypropylene product, and different antibacterial master batches are added, specifically described as follows:
(1)10kg of polypropylene (melt index of 1.6g/min), adding polypropylene wax-based antibacterial materials with different contents, carrying out melt blending on a double-screw extruder, cooling, 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 ℃.
Therefore, in the present invention, when the amount of the antibacterial mother particles exceeds 1%, an excellent antibacterial activity 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 polypropylene wax-based nano-silver antibacterial material is characterized by comprising the following steps: firstly, preparing sulfhydrylation polypropylene wax, then uniformly mixing the sulfhydrylation modified polypropylene wax and the nano-silver antibacterial agent to obtain the polypropylene wax-based nano-silver antibacterial material.
2. The method for preparing the polypropylene wax-based nano-silver antibacterial material as claimed in 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 polypropylene wax-based nano-silver antibacterial material as claimed in 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 polypropylene wax-based nano-silver antibacterial material as claimed in claim 1, wherein the method comprises the following steps: in the preparation of the sulfhydrylation polypropylene wax, the polypropylene wax is firstly subjected to epoxidation modification, and then mercaptoethylamine is added into the polypropylene wax subjected to epoxidation modification to obtain the sulfhydrylation polypropylene wax.
5. The method for preparing the polypropylene wax-based nano-silver antibacterial material as claimed in claim 1 or 4, wherein the method comprises the following steps: the mercapto-modified polypropylene wax has a mercapto to epoxy molar ratio of 0.2 to 0.9.
6. The method for preparing the polypropylene wax-based nano-silver antibacterial material as claimed in claim 1, wherein the method comprises the following steps: in the polypropylene wax-based nano silver antibacterial material, the silver content is 10-35 wt%.
7. The method for preparing the polypropylene wax-based nano-silver antibacterial material as claimed in claim 1, wherein the method comprises the following steps: the number average molecular weight of the polypropylene wax is 8000-.
8. The method for preparing the polypropylene wax-based nano-silver antibacterial material as claimed in claim 1, wherein the basic structural formula of the polypropylene wax-based nano-silver antibacterial material is as follows:
9. the use of the polypropylene wax-based nano silver antibacterial material as claimed in claim 1 in polypropylene injection-molded products, wherein: the polypropylene wax-based nano silver antibacterial material is used for injection molding of polypropylene products, and is subjected to melt blending with polypropylene resin and then injection molding.
10. The use of the polypropylene wax-based nano-silver antibacterial material as claimed in claim 9 in polypropylene injection-molded articles, wherein: the melt index of the polypropylene resin is between 1.2 and 5.6 g/min.
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