CN111636112A - Graphene composite antibacterial and antiviral polypropylene filament and preparation method thereof - Google Patents
Graphene composite antibacterial and antiviral polypropylene filament and preparation method thereof Download PDFInfo
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- CN111636112A CN111636112A CN202010580102.0A CN202010580102A CN111636112A CN 111636112 A CN111636112 A CN 111636112A CN 202010580102 A CN202010580102 A CN 202010580102A CN 111636112 A CN111636112 A CN 111636112A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 135
- -1 polypropylene Polymers 0.000 title claims abstract description 111
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 110
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 50
- 238000009987 spinning Methods 0.000 claims description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- 229960003964 deoxycholic acid Drugs 0.000 claims description 4
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004299 exfoliation Methods 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- 229920013822 aminosilicone Polymers 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 15
- 241000894006 Bacteria Species 0.000 abstract 1
- 241000700605 Viruses Species 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000002788 crimping Methods 0.000 description 5
- 230000002155 anti-virotic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LOJPEGWUHVRGBN-UHFFFAOYSA-J tetrachlorotitanium;triethylalumane Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].CC[Al](CC)CC LOJPEGWUHVRGBN-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Abstract
The invention discloses a graphene composite antibacterial antiviral polypropylene filament and a preparation method thereof, wherein the graphene composite antibacterial antiviral polypropylene filament comprises the following raw materials in percentage by mass: 90-95% of propylene monomer, 0.1-9% of graphene material, 0.1-5% of first modifier, 0.1-5% of second modifier and 0.1-1% of catalyst. The invention also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament. The modified graphene polypropylene filament fiber with the functions of resisting bacteria and viruses, removing formaldehyde and the like can be prepared, the additional value of the polypropylene fiber is improved, the application range of the polypropylene fiber is expanded, graphene in the prepared in-situ polymerization modified graphene polypropylene filament is uniformly dispersed and is not easy to fall off, the functionality is durable, the performance is excellent, the requirement of the current market on the functionalized graphene polypropylene filament fiber can be met, and the application prospect is wide.
Description
Technical Field
The invention relates to a graphene composite polypropylene filament and a preparation method thereof, and particularly relates to a graphene composite antibacterial antiviral polypropylene filament and a preparation method thereof.
Background
Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, researchers have not found that graphene has a missing carbon atom, the linkage between carbon atoms is very flexible, and is harder than diamond, the strength is 100 times higher than that of the world's best steel, if graphene is used for making a packaging bag, the graphene can bear about two tons of articles, the graphene is almost completely transparent, but is very compact, waterproof and airtight, helium gas with the minimum atomic size cannot pass through the graphene, the graphene has good conductivity, the movement speed of electrons in graphene reaches 1/300 of the light speed, the conductivity exceeds that of any traditional conductive material, the chemical properties are similar to the surface of graphite, various atoms and molecules can be adsorbed and desorbed, and the graphene also has the capability of resisting strong acid and strong alkali.
The polypropylene fiber is a chemical fiber with low cost, good performance and extremely wide application, but the traditional polypropylene fiber has no functionality, and along with the social development, the traditional polypropylene fiber can not meet the requirements of people on functional textiles.
Disclosure of Invention
The invention aims to provide a graphene composite polypropylene filament and a preparation method thereof, wherein a modified graphene oxide solution preparation and dispersion system and a polypropylene in-situ polymerization technology are utilized, the composite filament has the characteristics of antibiosis, antivirus, formaldehyde removal and the like, graphene in the in-situ polymerization modified graphene polypropylene filament is uniformly dispersed and is not easy to fall off, and the functionality has durability.
In order to achieve the purpose, the invention provides a graphene composite antibacterial and antiviral polypropylene filament, wherein the raw materials of the polypropylene filament comprise, by mass: 90-95% of propylene monomer, 0.1-9% of graphene material, 0.1-5% of first modifier, 0.1-5% of second modifier and 0.1-1% of catalyst.
The graphene composite antibacterial and antiviral polypropylene filament is characterized in that the graphene material comprises any one of graphene or graphene oxide prepared by a mechanical stripping method, a chemical vapor deposition method and a redox method.
The graphene composite antibacterial and antiviral polypropylene filament comprises a first modifier and a second modifier, wherein the first modifier comprises one or more of polyvinyl alcohol, hydroxypropyl cellulose, polyethylene glycol, sodium lignosulfonate, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, sodium deoxycholate, aminosiloxane, octadecylamine and a silane coupling agent.
The graphene composite antibacterial and antiviral polypropylene filament is characterized in that the second modifier comprises one or more of diethylenetriamine, sodium hexametaphosphate, lysine, ferric nitrate, basic copper carbonate, potassium iodide and sodium thiosulfate.
The graphene composite antibacterial and antiviral polypropylene filament is characterized in that the catalyst is any one or two of a metallocene catalyst and a Z-N catalyst.
The invention also provides a preparation method of the graphene composite antibacterial and antiviral polypropylene filament, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing modified graphene oxide slurry, and freeze-drying to obtain modified graphene oxide powder; step 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture; step 4, carrying out polymerization reaction, then discharging, granulating and drying to obtain in-situ polymerized graphene polypropylene master batches; and 5, drying the graphene polypropylene master batch obtained in the step 4, adding the dried graphene polypropylene master batch into a screw extruder for heating and melting, filtering the obtained product through a spinning box, spinning the obtained product into bundles to obtain modified graphene polypropylene composite fibers, and stretching and curling the modified graphene polypropylene composite fibers to obtain the modified graphene polypropylene composite filaments used under different conditions.
In the step 2, the graphene material, the first modifier and the second modifier are added into deionized water, the mixture is stirred for 0.5-1 h, then the temperature is increased to 50-80 ℃, ultrasonic dispersion treatment is carried out for 10-20 min, modified graphene oxide slurry is prepared, freeze drying is carried out to obtain modified graphene oxide powder, the powder is sent into a container to be sealed, vacuumized and then filled with nitrogen for protection for later use.
The preparation method of the graphene composite antibacterial antiviral polypropylene filament comprises the following steps of preparing a graphene material, and preparing a graphene oxide powder from the graphene material.
In the step 4, the propylene/modified graphene oxide mixture obtained in the step 3 is placed into a polymerization kettle, a catalyst is added, the mixture is heated to 50-60 ℃, stirred for 10-20 min, the temperature is raised to 70-90 ℃, the polymerization reaction is carried out for 3-5 h, and the in-situ polymerized graphene polypropylene master batch is obtained after discharging, cutting and drying.
In the step 5, the graphene polypropylene master batch is dried, the drying temperature is controlled within the range of 80-200 ℃, the water content of the master batch is controlled below 100ppm, the master batch is added into a screw extruder for heating and melting, and the obtained product is filtered by a spinning box and spun into bundles, so that the modified graphene polypropylene composite fiber is obtained, wherein the spinning temperature is 210-280 ℃, and the spinning speed is 500-1500 m/min.
The graphene composite antibacterial and antiviral polypropylene filament and the preparation method thereof provided by the invention have the following advantages:
according to the invention, graphene oxide is adopted, modified graphene oxide powder is prepared firstly, and then is subjected to compound copolymerization with propylene to prepare graphene polypropylene master batches, and the composite master batches are subjected to melt spinning equipment to prepare the functional graphene composite polypropylene filament.
The in-situ polymerized graphene-polypropylene composite filament has excellent performances of antibiosis, antivirus, formaldehyde removal and the like, meets the requirements of the current market on functionalized graphene-polypropylene filament fibers, and has wide application prospect.
The graphene composite antibacterial and antiviral polypropylene filament prepared by the method is simple in process, easy to operate, low in cost, high in economic benefit and suitable for large-scale industrial production.
Detailed Description
The following further describes embodiments of the present invention.
The graphene composite antibacterial and antiviral polypropylene filament provided by the invention comprises the following raw materials in percentage by mass: 90-95% of propylene monomer, 0.1-9% of graphene material, 0.1-5% of first modifier, 0.1-5% of second modifier and 0.1-1% of catalyst.
Preferably, the graphene material includes any one of graphene or graphene oxide prepared by a mechanical exfoliation method, a chemical vapor deposition method, a redox method, and the like.
The first modifier comprises one or more of polyvinyl alcohol, hydroxypropyl cellulose, polyethylene glycol, sodium lignosulfonate, polyvinylpyrrolidone (PVP), sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, sodium deoxycholate, aminosiloxane, octadecylamine, silane coupling agent, etc.
The second modifier comprises one or more of diethylenetriamine, sodium hexametaphosphate, lysine, ferric nitrate, basic copper carbonate, potassium iodide, sodium thiosulfate and the like.
The catalyst is one or two of metallocene catalyst, Z-N catalyst, etc.
The metallocene catalyst is a catalyst system which is composed of IVB group transition metal element complex as a main catalyst and alkyl aluminoxane or organic boride) as a cocatalyst and has high activity of catalyzing ethylene polymerization.
Z-N catalysts, Ziegler-Natta catalysts, are catalysts for the synthesis of unbranched, highly stereoregular polyolefins, typical Ziegler-Natta catalysts are two-component: titanium tetrachloride-triethylaluminium.
The invention also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps: step 1, weighing raw materials in proportion; step 2, preparing modified graphene oxide slurry, and freeze-drying to obtain modified graphene oxide powder; step 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture; step 4, carrying out polymerization reaction, then discharging, granulating and drying to obtain in-situ polymerized graphene polypropylene master batches; and 5, drying the graphene polypropylene master batch obtained in the step 4, adding the dried graphene polypropylene master batch into a screw extruder for heating and melting, filtering the obtained product through a spinning box, spinning the obtained product into bundles to obtain modified graphene polypropylene composite fibers, namely modified graphene polypropylene composite fibers, and stretching and curling the modified graphene polypropylene composite fibers to obtain the modified graphene polypropylene composite filaments used under different conditions.
In the step 2, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then raising the temperature to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch, controlling the drying temperature to be within the range of 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, and then spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, and the spinning speed is 500-1500 m/min.
The graphene composite antibacterial and antiviral polypropylene filament and the preparation method thereof provided by the invention are further described below with reference to the examples.
Example 1
The graphene composite antibacterial and antiviral polypropylene filament comprises the following raw materials in percentage by mass: 95% of propylene monomer, 0.1% of graphene material, 0.1% of first modifier, 3.8% of second modifier and 1% of catalyst.
Preferably, the graphene material comprises graphene or graphene oxide prepared using a mechanical exfoliation method.
The first modifier comprises polyvinyl alcohol, hydroxypropyl cellulose and polyethylene glycol.
The second modifier comprises diethylenetriamine.
The catalyst is a metallocene catalyst.
The embodiment also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing modified graphene oxide slurry, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then heating to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing the modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch obtained in the step 4, controlling the drying temperature to be 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, the spinning speed is 500-1500m/min, and obtaining the modified graphene polypropylene composite filament used under different conditions through drawing and crimping processes.
Example 2
The graphene composite antibacterial and antiviral polypropylene filament comprises the following raw materials in percentage by mass: 91% of propylene monomer, 2% of graphene material, 5% of first modifier, 1.2% of second modifier and 0.8% of catalyst.
Preferably, the graphene material comprises graphene or graphene oxide prepared by a chemical vapor deposition method.
The first modifier comprises sodium lignosulfonate or polyvinylpyrrolidone.
The second modifier comprises sodium hexametaphosphate or lysine.
The catalyst is Z-N catalyst.
The embodiment also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing modified graphene oxide slurry, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then heating to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing the modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch obtained in the step 4, controlling the drying temperature to be 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, the spinning speed is 500-1500m/min, and obtaining the modified graphene polypropylene composite filament used under different conditions through drawing and crimping processes.
Example 3
The graphene composite antibacterial and antiviral polypropylene filament comprises the following raw materials in percentage by mass: 90.4% of propylene monomer, 3% of graphene material, 1% of first modifier, 5% of second modifier and 0.6% of catalyst.
Preferably, the graphene material comprises graphene or graphene oxide prepared by a redox method.
The first modifier comprises sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The second modifier comprises iron nitrate and basic copper carbonate.
The catalyst is Z-N catalyst.
The embodiment also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing modified graphene oxide slurry, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then heating to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing the modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch obtained in the step 4, controlling the drying temperature to be 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, the spinning speed is 500-1500m/min, and obtaining the modified graphene polypropylene composite filament used under different conditions through drawing and crimping processes.
Example 4
The graphene composite antibacterial and antiviral polypropylene filament comprises the following raw materials in percentage by mass: 92.5% of propylene monomer, 5% of graphene material, 1% of first modifier, 1% of second modifier and 0.5% of catalyst.
Preferably, the graphene material comprises graphene or graphene oxide prepared by a mechanical exfoliation method or a chemical vapor deposition method.
The first modifier comprises cetyltrimethylammonium bromide or sodium deoxycholate.
The second modifier comprises potassium iodide.
The catalyst is a metallocene catalyst.
The embodiment also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing modified graphene oxide slurry, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then heating to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing the modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch obtained in the step 4, controlling the drying temperature to be 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, the spinning speed is 500-1500m/min, and obtaining the modified graphene polypropylene composite filament used under different conditions through drawing and crimping processes.
Example 5
The graphene composite antibacterial and antiviral polypropylene filament comprises the following raw materials in percentage by mass: 90% of propylene monomer, 9% of graphene material, 0.5% of first modifier, 0.4% of second modifier and 0.1% of catalyst.
Preferably, the graphene material comprises graphene or graphene oxide prepared by a chemical vapor deposition method or a redox method.
The first modifier comprises aminosiloxane, octadecylamine and a silane coupling agent.
The second modifier comprises any one or more of sodium thiosulfate.
The catalyst is one or two of metallocene catalyst and Z-N catalyst.
The embodiment also provides a preparation method of the graphene composite antibacterial antiviral polypropylene filament, which comprises the following steps:
step 1, weighing the raw materials in proportion.
And 2, preparing modified graphene oxide slurry, adding a graphene material, a first modifier and a second modifier into deionized water, stirring for 0.5-1 h, then heating to 50-80 ℃, performing ultrasonic dispersion treatment for 10-20 min, preparing the modified graphene oxide slurry, freeze-drying to obtain modified graphene oxide powder, conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection for later use.
The graphene material is preferably graphene oxide powder.
And 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture.
And 4, putting the propylene/modified graphene oxide mixture obtained in the step 3 into a polymerization kettle, adding a catalyst, heating to 50-60 ℃, stirring for 10-20 min, raising the temperature to 70-90 ℃, carrying out polymerization reaction for 3-5 h, discharging, granulating and drying to obtain the in-situ polymerized graphene polypropylene master batch.
And 5, drying the graphene polypropylene master batch obtained in the step 4, controlling the drying temperature to be 80-200 ℃, controlling the water content of the master batch to be below 100ppm, adding the master batch into a screw extruder for heating and melting, filtering the master batch through a spinning box, spinning the master batch into bundles to obtain the modified graphene polypropylene composite fiber, wherein the spinning temperature is 210-280 ℃, the spinning speed is 500-1500m/min, and obtaining the modified graphene polypropylene composite filament used under different conditions through drawing and crimping processes.
The invention provides a graphene composite antibacterial and antiviral polypropylene filament and a preparation method thereof, and aims to prepare a modified graphene polypropylene filament fiber with antibacterial, antiviral, formaldehyde removing and other functions, improve the additional value of the polypropylene fiber and expand the application range of the polypropylene fiber. The characteristic technology is that the modified graphene oxide powder is prepared by using graphene oxide, then the modified graphene oxide powder is subjected to composite copolymerization with propylene, and then the modified graphene oxide powder is placed into a reaction kettle for reaction, and then the reaction kettle is discharged, granulated and finally subjected to melt spinning. The prepared graphene polypropylene filament fiber has good antibacterial property, antivirus, formaldehyde removal and other functions, the original polymerized graphene polypropylene is permanent in functionality, the condition that the functionality is weakened along with the increase of washing times is avoided, the application range of the traditional polypropylene is expanded, the added value of products is improved, and the requirements of people on healthy and environment-friendly functional textiles are well met.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. The graphene composite antibacterial and antiviral polypropylene filament is characterized by comprising the following raw materials in percentage by mass: 90-95% of propylene monomer, 0.1-9% of graphene material, 0.1-5% of first modifier, 0.1-5% of second modifier and 0.1-1% of catalyst.
2. The graphene composite antibacterial and antiviral polypropylene filament according to claim 1, wherein the graphene material comprises any one of graphene or graphene oxide prepared by a mechanical exfoliation method, a chemical vapor deposition method and a redox method.
3. The graphene composite antibacterial and antiviral polypropylene filament according to claim 1, wherein the first modifier comprises any one or more of polyvinyl alcohol, hydroxypropyl cellulose, polyethylene glycol, sodium lignosulfonate, polyvinylpyrrolidone, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, cetyltrimethylammonium bromide, sodium deoxycholate, aminosilicone, octadecylamine and silane coupling agent.
4. The graphene composite antibacterial and antiviral polypropylene filament according to claim 1, wherein the second modifier comprises one or more of diethylenetriamine, sodium hexametaphosphate, lysine, ferric nitrate, basic copper carbonate, potassium iodide, and sodium thiosulfate.
5. The graphene composite antibacterial and antiviral polypropylene filament according to claim 1, wherein the catalyst is one or both of a metallocene catalyst and a Z-N catalyst.
6. A preparation method of the graphene composite antibacterial and antiviral polypropylene filament as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
step 1, weighing raw materials in proportion;
step 2, preparing modified graphene oxide slurry, and freeze-drying to obtain modified graphene oxide powder;
step 3, adding the modified graphene oxide powder obtained in the step 2 into propylene, and uniformly stirring to prepare a propylene/modified graphene oxide mixture;
step 4, carrying out polymerization reaction, then discharging, granulating and drying to obtain in-situ polymerized graphene polypropylene master batches;
and 5, drying the graphene polypropylene master batch obtained in the step 4, adding the dried graphene polypropylene master batch into a screw extruder for heating and melting, filtering the obtained product through a spinning box, spinning the obtained product into bundles to obtain modified graphene polypropylene composite fibers, and stretching and curling the modified graphene polypropylene composite fibers to obtain the modified graphene polypropylene composite filaments used under different conditions.
7. The preparation method of the graphene composite antibacterial and antiviral polypropylene filament according to claim 6, wherein in the step 2, the graphene material, the first modifier and the second modifier are added into deionized water, stirred for 0.5-1 h, then the temperature is raised to 50-80 ℃, ultrasonic dispersion treatment is carried out for 10-20 min, modified graphene oxide slurry is prepared, freeze drying is carried out to obtain modified graphene oxide powder, the modified graphene oxide powder is sent into a container, sealed and vacuumized, and then nitrogen gas is filled for protection for later use.
8. The method for preparing the graphene composite antibacterial and antiviral polypropylene filament according to claim 7, wherein the graphene material is graphene oxide powder.
9. The preparation method of the graphene composite antibacterial antiviral polypropylene filament according to claim 6, wherein in the step 4, the propylene/modified graphene oxide mixture obtained in the step 3 is placed into a polymerization kettle, a catalyst is added, the mixture is heated to 50-60 ℃, stirred for 10-20 min, the temperature is raised to 70-90 ℃, the polymerization reaction is carried out for 3-5 h, and the in-situ polymerized graphene polypropylene master batch is obtained after discharging, granulating and drying.
10. The method for preparing the graphene composite antibacterial and antiviral polypropylene filament according to claim 6, wherein in the step 5, the graphene polypropylene master batch is dried, the drying temperature is controlled within the range of 80-200 ℃, the water content of the master batch is controlled below 100ppm, the dried master batch is added into a screw extruder for heating and melting, the obtained product is filtered by a spinning manifold and then spun into bundles, and the modified graphene polypropylene composite fiber is obtained, wherein the spinning temperature is 210-280 ℃, and the spinning speed is 500-1500 m/min.
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