CN111333956A - Antibacterial polypropylene material and preparation method thereof - Google Patents
Antibacterial polypropylene material and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 63
- -1 polypropylene Polymers 0.000 title claims abstract description 53
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 52
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920001661 Chitosan Polymers 0.000 claims abstract description 54
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims abstract description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000001069 triethyl citrate Substances 0.000 claims abstract description 15
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000013769 triethyl citrate Nutrition 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 10
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003242 anti bacterial agent Substances 0.000 description 12
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241000233866 Fungi Species 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
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- 244000052616 bacterial pathogen Species 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 238000013518 transcription Methods 0.000 description 1
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Classifications
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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
-
- 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
- C08K2003/0806—Silver
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides an antibacterial polypropylene material and a preparation method thereof, and the antibacterial polypropylene material comprises the following raw materials: the homopolymerized polypropylene resin, the filler nano calcium carbonate and the toughening agentEthylene-1-octene copolymer, nano-silver, dispersant TAS-2A, antioxidant, triethyl citrate, sulfosalicylic acid La complex, chitosan and nano-La2O3(ii) a The mass ratio of the sulfosalicylic acid La complex to the chitosan is 0.05-0.1:5-10, and the La is2O3The mass ratio of the silver to the nano silver is 1: 1; the average grain diameter of the chitosan is 20-50 nm; the preparation method comprises the steps of pre-dispersing, mixing, extruding and the like. The invention provides an antibacterial polypropylene material and a preparation method thereof, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, improves the mechanical strength and the thermal deformation temperature, and reduces the shrinkage rate by adding the rare earth complex, the oxide and the chitosan.
Description
Technical Field
The invention belongs to the field of modified plastics, and particularly relates to an antibacterial polypropylene material and a preparation method thereof.
Background
Polypropylene (PP) is one of five general-purpose plastics, has the density of 0.90g/cm3, and is the second-lightest polymer material (the density of 0.85g/cm, which is only larger than that of polymethylpentene) of the existing resin.
In daily life, polypropylene plastic products are widely used: such as kitchen utensils, toilet facilities, garbage cans, plastic shells of household appliances, wallpaper, food packaging bags and the like. Due to proper temperature and humidity, bacteria are easily infected. Therefore, it is very necessary to develop an antibacterial polypropylene material.
At present, two methods of filling and post-processing are mainly used for preparing the antibacterial polypropylene material. The filling type is formed by melting, blending, extruding and granulating the antibacterial agent and the PP resin; the polypropylene material is processed into a product, then the antibacterial agent is combined on the surface of the product through a chemical bond or a hydrogen bond, and the antibacterial agent is not arranged in the product.
In the manufacturing method of the filling type antibacterial polypropylene material, the selection of the antibacterial agent is important, and the antibacterial agent is divided into two categories of inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent has the advantages of antibacterial persistence, heat resistance, durability, safety and the like, and has the defects of higher price, antibacterial slow effect and incapability of quickly killing bacteria; the organic antibacterial agent can effectively inhibit the generation and reproduction of harmful bacteria and mould, but has short action time, is harmful to human bodies, is easy to hydrolyze, and can only be used below 300 ℃.
The chitosan and its derivatives have good antibacterial activity, and can inhibit growth and reproduction of fungi, bacteria and viruses. By 2013, the possible mechanisms are considered to be three: firstly, due to polycation of chitosan, the surface of fungal cell is easy to have the action of negatively charged groups, so that the fluidity and permeability of the cell membrane of pathogenic bacteria are changed; secondly, the replication and the transcription of DNA are interfered; and thirdly, the metabolism of pathogenic bacteria is blocked. Since 2010, many researchers have proposed that chitosan could achieve antibacterial effects by inducing disease-related proteins, accumulating secondary metabolites and conducting signals.
CN103059405A discloses an antibacterial polypropylene plastic, which utilizes chitosan as an antibacterial agent, but the antibacterial property and the mechanical property of the prepared polypropylene plastic are still to be improved. CN101089038B discloses an antibacterial polypropylene plastic, which adopts nano silver and an organosilicon antibacterial agent as antibacterial agents, and can obtain good antibacterial effect, but the mechanical properties of the antibacterial polypropylene plastic are not improved at all. Therefore, an antibacterial polypropylene plastic is urgently needed, and the mechanical property can be synchronously improved while the antibacterial effect is improved.
Disclosure of Invention
The invention provides an antibacterial polypropylene material and a preparation method thereof, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, improves the mechanical strength and the thermal deformation temperature, and reduces the shrinkage rate by adding the rare earth complex, the oxide and the chitosan.
The purpose of the invention is realized by the following technical scheme:
an antibacterial polypropylene material, which comprises the following raw materials: homo-polypropylene resin, filler nano calcium carbonate, toughening agent ethylene-1-octene copolymer, nano silver, dispersant TAS-2A, antioxidant, triethyl citrate, sulfosalicylic acid La complex, chitosan, La2O3(ii) a The mass ratio of the sulfosalicylic acid La complex to the chitosan is 0.05-0.1:5-10, and the La is2O3The mass ratio of the silver to the nano silver is 1: 1; the average grain diameter of the chitosan is 20-50 nm.
Further, the antibacterial polypropylene material is characterized by comprising the following raw materials: 100 parts by mass of homopolymerized polypropylene resin, 25-35 parts by mass of filler nano calcium carbonate, 5-15 parts by mass of toughening agent ethylene-1-octene copolymer, 0.2-0.8 part by mass of nano silver, 0.5-1.5 parts by mass of dispersing agent TAS-2A, 0.1-0.5 part by mass of antioxidant, 0.1-0.5 part by mass of triethyl citrate, 0.05-0.1 part by mass of sulfosalicylic acid La complex, 5-10 parts by mass of chitosan, 0.2-0.8 part by mass of La2O3。
Further, the mass ratio of the sulfosalicylic acid La complex to the chitosan is 0.08:8
Further, the antioxidant is one or more of antioxidants 1076, 1010 and 164.
Further, wherein La2O3Has an average particle diameter of 20 to 50 nm.
The invention also provides a preparation method of the antibacterial polypropylene material, which comprises the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, the nano silver, the dispersant TAS-2A, the antioxidant, the triethyl citrate and the La according to the weight ratio2O3Mixing the powder obtained in the step 1 in a high-speed mixer;
(3) and putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation.
Further, the extrusion process of the parallel twin-screw extruder comprises the following steps: the first zone is 170-180 ℃, the second zone is 180-190 ℃, the third zone is 180-190 ℃, the fourth zone is 175-185 ℃, the screw rotation speed is 300-350r/min, the feeding frequency is 15-20Hz, the melt pressure is 3.0-4.0MPa, and the vacuum degree is-0.03-0.06 MPa.
Further, the components in step 2 are mixed in a high speed mixer for 3-5 minutes.
The chitosan has antibacterial effect, and has inhibitory effect on algae, bacteria, fungi, etc., and the sterilization mechanism of the chitosan is probably polycation of the chitosan, and the chitosan is easy to generate effect with surface negative charges of the fungi. The polypropylene material can have a certain antibacterial property by adding the chitosan into the polypropylene, and in order to maximize the antibacterial effect of the chitosan, the particle size of the chitosan is 20-50 nm. Too large particle size will result in difficult dispersion in the polymer, uneven dispersion will reduce the mechanical properties of the polymer, too small particle size chitosan will easily agglomerate, and the price is high.
The sulfosalicylic acid La complex is a rare earth ternary complex and has a strong broad-spectrum antibacterial effect, after the antibacterial effect of the sulfosalicylic acid La complex is combined with a chelating effect organic ligand of the ligand and rare earth metal ions to form the complex, the positive charge of the rare earth ions is partially transferred to the organic ligand, electrons on a chelate ring generate a delocalization effect, so that the polarity of the metal ions is reduced, the fat solubility of the complex is enhanced, and the complex can better penetrate through a lipid-like layer of a biological cell membrane, so that the normal metabolism of cells is influenced. Due to the electronic effect, the sulfosalicylic acid La complex can be loaded on nano-level chitosan to increase the dispersibility of the chitosan, and groups with coordination capacity, such as-NH 2, -OH and the like, contained in the chitosan can form cage-shaped molecules with a similar net structure by virtue of hydrogen bonds or salt bonds, and can be very easily coordinated with rare earth metals, so that a synergistic effect is generated, the sulfosalicylic acid La complex can be more easily dispersed and quickly contacted with bacteria, and the high-efficiency antibacterial effect is realized. In the preparation process, the sulfosalicylic acid La complex and the chitosan are dispersed in ethanol in advance, and are refluxed for a period of time, so that the sulfosalicylic acid La complex and the chitosan can be fully promoted to be matched and dispersed, and the performance of a final product is improved.
The reticular molecules formed by the chitosan can play a further supporting effect in the polymer material, so that the mechanical property of the polymer material is improved, and the shrinkage rate is reduced. The rare earth complex can be used as a heat stabilizer, so that the heat distortion temperature is increased. The rare earth complex and chitosan have certain alkalescence, and can effectively remove a small amount of acidic substances of the polymer, thereby improving the mechanical strength of the polymer.
The rare earth oxide has rich and various electronic energy levels and spectral lines compared with other elements, can absorb or emit in ultraviolet light, visible light and infrared light regions, and is a very good substance with wide color spectrum. Lanthanum oxide itself has certain bactericidal properties due to the specific properties of its rare earth. After the lanthanum oxide is added, the lanthanum oxide can be matched with the nano silver oxide for use, so that the antibacterial property of the nano silver oxide is further improved through the broad-spectrum excitation performance of the lanthanum oxide. The addition of lanthanum oxide and nano silver oxide at a ratio of 1:1 can achieve the maximum antibacterial effect. Meanwhile, the rare earth oxide has a very high melting point, and can be used as a crystal core to increase the thermal deformation temperature by adding a small amount of the rare earth oxide.
The invention has the beneficial technical effects that:
the invention provides an antibacterial polypropylene material and a preparation method thereof, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, improves the mechanical strength and the thermal deformation temperature, and reduces the shrinkage rate by adding the rare earth complex, the oxide and the chitosan.
Detailed Description
The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.
An antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 25-35 parts by mass of filler nano calcium carbonate, 5-15 parts by mass of toughening agent ethylene-1-octene copolymer, 0.2-0.8 part by mass of nano silver, 0.5-1.5 parts by mass of dispersing agent TAS-2A, 0.1-0.5 part by mass of antioxidant 1076, 0.1-0.5 part by mass of triethyl citrate, 0.05-0.1 part by mass of sulfosalicylic acid La complex, 5-10 parts by mass of chitosan, 0.2-0.8 part by mass of La2O3. The La2O3The mass ratio of the silver to the nano silver is 1: 1; the average grain diameter of the chitosan is 20-50 nm.
The preparation method of the sulfosalicylic acid La complex is prepared according to the method disclosed in' Lixiafang, Von Xiaoqiang, Yang sound, and the like, lanthanum-sulfosalicylic acid-8-hydroxyquinoline ternary complex synthesis, characterization and bacteriostasis [ J ]. synthetic fiber, 2010, 39(7):30-33 ].
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, the nano silver, the dispersant TAS-2A, the antioxidant, the triethyl citrate and the La according to the weight ratio2O3Mixing the powder obtained in the step 1 in a high-speed mixer for 3-5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process of the parallel double-screw extruder comprises the following steps: 170 ℃ in the first zone, 180 ℃ in the second zone, 180 ℃ in the third zone, 175 ℃ in the fourth zone, 300r/min of screw rotation speed, 15Hz of feeding frequency, 3.0MPa of melt pressure and 0.03MPa of vacuum degree.
Example 1
An antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 30 parts by mass of filler nano calcium carbonate, 10 parts by mass of toughening agent ethylene-1-octene copolymer, 0.6 part by mass of nano silver, 1.0 part by mass of dispersing agent TAS-2A, 0.3 part by mass of antioxidant 1076, 0.3 part by mass of triethyl citrate, 0.08 part by mass of sulfosalicylic acid La complex, 8 parts by mass of chitosan, and 0.6 part by mass of La2O3. The average grain diameter of the chitosan is 20-50 nm.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, the nano silver, the dispersant TAS-2A, the antioxidant, the triethyl citrate and the La according to the weight ratio2O3Mixing the powder obtained in the step 1 in a high-speed mixer for 3-5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process of the parallel double-screw extruder comprises the following steps: 170 ℃ in the first zone, 180 ℃ in the second zone, 180 ℃ in the third zone, 175 ℃ in the fourth zone, 300r/min of screw rotation speed, 15Hz of feeding frequency, 3.0MPa of melt pressure and 0.03MPa of vacuum degree.
Example 2
An antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 25 parts by mass of filler nano calcium carbonate, 15 parts by mass of toughening agent ethylene-1-octene copolymer, 0.2 part by mass of nano silver, 1.5 parts by mass of dispersing agent TAS-2A and 0.1 part by mass of antioxidant 1076. 0.5 part by mass of triethyl citrate, 0.05 part by mass of sulfosalicylic acid La complex, 10 parts by mass of chitosan, and 0.2 part by mass of La2O3. The average grain diameter of the chitosan is 20-50 nm.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, the nano silver, the dispersant TAS-2A, the antioxidant, the triethyl citrate and the La according to the weight ratio2O3Mixing the powder obtained in the step 1 in a high-speed mixer for 3-5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process of the parallel double-screw extruder comprises the following steps: 170 ℃ in the first zone, 180 ℃ in the second zone, 180 ℃ in the third zone, 175 ℃ in the fourth zone, 300r/min of screw rotation speed, 15Hz of feeding frequency, 3.0MPa of melt pressure and 0.03MPa of vacuum degree.
Example 3
An antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 35 parts by mass of filler nano calcium carbonate, 5 parts by mass of toughening agent ethylene-1-octene copolymer, 0.8 part by mass of nano silver, 0.5 part by mass of dispersing agent TAS-2A, 0.5 part by mass of antioxidant 1076, 0.1 part by mass of triethyl citrate, 0.1 part by mass of sulfosalicylic acid La complex, 5 parts by mass of chitosan, and 0.8 part by mass of La2O3. The average grain diameter of the chitosan is 20-50 nm.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, nano silver and the mixture according to the weight ratio,Dispersant TAS-2A, antioxidant, triethyl citrate and La2O3Mixing the powder obtained in the step 1 in a high-speed mixer for 3-5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process of the parallel double-screw extruder comprises the following steps: 170 ℃ in the first zone, 180 ℃ in the second zone, 180 ℃ in the third zone, 175 ℃ in the fourth zone, 300r/min of screw rotation speed, 15Hz of feeding frequency, 3.0MPa of melt pressure and 0.03MPa of vacuum degree.
Comparative example 1
Prepared in the same manner as in example 1, except that the sulfosalicylic acid La complex, chitosan, La2O3 were not added.
Comparative example 2
Prepared in the same manner as in example 1, except that the sulfosalicylic acid La complex was not added.
Comparative example 3
Prepared in the same manner as in example 1, except that chitosan was not added.
Comparative example 4
Prepared in the same manner as in example 1, except that La2O3 was not added.
Comparative example 5
Prepared in the same manner as in example 1, except that La2O3Is 1.2 parts by mass.
Comparative example 6
Prepared in the same manner as in example 1 except that chitosan was 16 parts by mass.
Comparative example 7
Prepared according to the method of example 2 disclosed in CN 101089038B.
The products prepared in the above examples and comparative examples are pressed into plates, plastic samples of 50mm × 50mm are prepared, and antibacterial tests are carried out, the test data are shown in Table 1, the antibacterial test standard is QB/T2591-2003A, antibacterial property test method and antibacterial effect of antibacterial plastics, the bacteria for detection is Escherichia coli (Escherichia coli) ATCC25922, shrinkage rate is measured according to an ASTMD955 method, tensile property is tested according to ISO527-93 requirements, the condition is 50mm/min, a FYWK-300 Vicat temperature tester is used for heat deformation temperature, the heating rate is 5 ℃/6min, and the measurement is carried out according to GB/T1633-2000 determination of the softening point temperature of the thermoplastic plastics Vicat.
TABLE 1 antibacterial Properties of examples and comparative examples
| Antibacterial ratio (%) | Tensile strength Mpa | Heat distortion temperature DEG C | Shrinkage (%) | |
| Example 1 | 100 | 46 | 163 | 0.6 |
| Example 2 | 100 | 44 | 159 | 0.7 |
| Example 3 | 100 | 43 | 156 | 0.7 |
| Comparative example 1 | 67 | 34 | 120 | 1.8 |
| Comparative example 2 | 82 | 39 | 138 | 1.2 |
| Comparative example 3 | 78 | 37 | 129 | 1.7 |
| Comparative example 4 | 86 | 41 | 126 | 1.0 |
| Comparative example 5 | 97 | 40 | 156 | 0.9 |
| Comparative example 6 | 95 | 42 | 142 | 0.6 |
| Comparative example 7 | 92 | 32 | 118 | 1.9 |
By comparing the properties, the antibacterial property and the mechanical property can be enhanced by adding the chitosan and the lanthanide series complex, the antibacterial property can be enhanced by adding the lanthanide series oxide, the heat distortion temperature and the mechanical property can be improved simultaneously, and the optimal effect cannot be realized by adding excessive chitosan or lanthanide series oxide, so that the optimal performance effect can be realized by the formula of the embodiment 1.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (8)
1. An antibacterial polypropylene material, which comprises the following raw materials: homo-polypropylene resin, filler nano calcium carbonate, toughening agent ethylene-1-octene copolymer, nano silver, dispersant TAS-2A, antioxidant, triethyl citrate, sulfosalicylic acid La complex, chitosan and nano La2O3(ii) a The mass ratio of the sulfosalicylic acid La complex to the chitosan is 0.05-0.1:5-10, and the La is2O3The mass ratio of the silver to the nano silver is 1: 1; the average grain diameter of the chitosan is 20-50 nm.
2. The antibacterial polypropylene material according to claim 1, wherein the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 25-35 parts by mass of filler nano calcium carbonate, 5-15 parts by mass of toughening agent ethylene-1-octene copolymer, 0.2-0.8 part by mass of nano silver, 0.5-1.5 parts by mass of dispersing agent TAS-2A, 0.1-0.5 part by mass of antioxidant, 0.1-0.5 part by mass of triethyl citrate, 0.05-0.1 part by mass of sulfosalicylic acid La complex, 5-10 parts by mass of chitosan, 0.2-0.8 part by mass of La2O3。
3. The antibacterial polypropylene material of claim 1, wherein the mass ratio of the sulfosalicylic acid La complex to the chitosan is 0.08: 8.
4. The antimicrobial polypropylene material of claim 1, wherein the antioxidant is one or more of antioxidants 1076, 1010, 164.
5. The antimicrobial polypropylene material of claim 1, wherein La2O3Has an average particle diameter of 20 to 50 nm.
6. A method for preparing the antibacterial polypropylene material according to claims 1-5, comprising the following steps:
(1) weighing the sulfosalicylic acid La complex and the chitosan according to the weight ratio, dispersing in ethanol, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing the homo-polypropylene resin, the filler nano calcium carbonate, the flexibilizer ethylene-1-octene copolymer, the nano silver, the dispersant TAS-2A, the antioxidant, the triethyl citrate and the La according to the weight ratio2O3Mixing the powder obtained in the step 1 in a high-speed mixer;
(3) and putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation.
7. The method for preparing the antibacterial polypropylene material according to claim 5, wherein the method comprises the following steps: the extrusion process of the parallel double-screw extruder comprises the following steps: the first zone is 170-180 ℃, the second zone is 180-190 ℃, the third zone is 180-190 ℃, the fourth zone is 175-185 ℃, the screw rotation speed is 300-350r/min, the feeding frequency is 15-20Hz, the melt pressure is 3.0-4.0MPa, and the vacuum degree is-0.03-0.06 MPa.
8. The method for preparing the antibacterial polypropylene material according to claim 5, wherein the method comprises the following steps: in the step 2, all components are mixed in a high-speed mixer for 3-5 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114711253A (en) * | 2021-01-06 | 2022-07-08 | 合肥杰事杰新材料股份有限公司 | Antibacterial agent, preparation method thereof and antibacterial composition |
| CN114855335A (en) * | 2022-06-18 | 2022-08-05 | 东莞市科纺纺织有限公司 | Polyurethane elastic fiber jean fabric and preparation method thereof |
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