CN117248371B - Preparation method of graphene antibacterial slurry - Google Patents
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- CN117248371B CN117248371B CN202311354966.0A CN202311354966A CN117248371B CN 117248371 B CN117248371 B CN 117248371B CN 202311354966 A CN202311354966 A CN 202311354966A CN 117248371 B CN117248371 B CN 117248371B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 230000006750 UV protection Effects 0.000 abstract description 8
- 238000004513 sizing Methods 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- -1 quaternary ammonium salt ion Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
- D06M15/09—Cellulose ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/13—Alginic acid or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of graphene antibacterial slurry, and belongs to the technical field of graphene materials. The modified graphene oxide is prepared by dispersing and mixing modified graphene oxide, a stabilizer and deionized water according to a mass ratio of 5-15:0.5-0.8:100. The stabilizer can enable the modified graphene oxide to be stably dispersed in the slurry, so that the performance can be fully exerted; the modified graphene oxide is obtained by grafting an organic molecular chain on the surface of the graphene oxide, and various functional groups in the molecular chain greatly improve the antibacterial property, antistatic property and hydrophilicity of the slurry; therefore, the prepared sizing agent has stable and efficient antibacterial property, hydrophilicity, and antistatic property and ultraviolet resistance to a certain extent, and has important application significance in the field of textile fabrics when being used as a finishing agent.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a preparation method of graphene antibacterial slurry.
Background
Graphene is a two-dimensional cellular planar structure formed by closely stacking single-layer carbon atoms. Its thickness is only 0.34nm, which is the thinnest known material in the world. The special structural characteristics enable the graphene to be a basic unit graphene for constructing carbon materials with other dimensions, and the graphene has excellent mechanical, electrical, thermal and barrier properties.
The sizing agent prepared by taking the graphene as a main active ingredient has important application value in the field of textile fabrics, the sizing agent is used as finishing liquid for finishing the fabrics, the antibacterial property, the ultraviolet resistance and the antistatic property of the finished fabrics can be improved, the cytotoxicity is 0 level, the sizing agent can be directly contacted with skin, the aim of pursuing higher performance of clothes by people is fulfilled, but the hydrophilicity and the biocompatibility of the graphene are poor, and the application field of the sizing agent is limited.
Graphene Oxide (GO) is a derivative of graphene, is a novel carbon material, has carboxylic acid functional groups at the edges and hydroxyl and epoxy groups on the surfaces, has good dispersibility, hydrophilicity, biocompatibility and other properties, and is considered as one of the most promising carbon materials in the current generation. However, the single antibacterial property and hydrophilicity of graphene oxide are still to be improved, and particularly when the graphene oxide is applied to the main active ingredient of the slurry, the antibacterial property and the dispersion stability in a solvent are required to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of graphene antibacterial slurry.
The aim of the invention can be achieved by the following technical scheme:
The preparation method of the graphene antibacterial slurry comprises the following steps:
A1, dispersing modified graphene oxide and a stabilizer in deionized water, wherein the linear speed of dispersion is 8m/s, and the dispersion is 120-160min;
A2, performing ultra-fine treatment on the mixture obtained in the first step, wherein the pressure is 55-75MPa, and finally performing vacuum defoaming to obtain graphene antibacterial slurry;
the prepared graphene antibacterial slurry adopts modified graphene oxide as a main active ingredient of the slurry, and can be uniformly and stably dispersed in the slurry under the action of a stabilizer, so that the antibacterial property, the ultraviolet resistance and the antistatic property of the graphene antibacterial slurry are fully exerted.
Further, the mass ratio of the modified graphene oxide, the stabilizer and the deionized water in the step A1 is 5-15:0.5-0.8:100.
Further, the stabilizer in the step A1 is one of sodium alginate, hydroxyethyl cellulose, sodium carboxymethyl cellulose and gelatin.
Further, the modified graphene oxide is prepared by the following steps:
s1, uniformly mixing allyl polyoxyethylene ether, trace hydrogen peroxide and chloroform in a three-neck flask with a stirring reflux device, controlling the reaction temperature at 60 ℃, slowly introducing hydrogen bromide gas, carrying out reflux reaction for 4 hours, and carrying out reduced pressure distillation to remove a solvent after the reaction is finished to obtain an intermediate 1; the ratio of the usage amount of the allyl polyoxyethylene ether to the usage amount of the hydrogen bromide gas is 0.1mol:0.1mol;
The hydrogen bromide and double bond are subjected to addition reaction, and anti-Mahalanobis addition is carried out under the action of trace hydrogen peroxide to obtain an intermediate 1; the specific reaction process is as follows:
S2, stirring and mixing the intermediate 1, ethylenediamine, triethylamine and tetrahydrofuran uniformly in a three-neck flask with a stirring device at room temperature under the protection of nitrogen, controlling the reaction temperature to be 75 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation, purifying by column chromatography (eluting solution adopts a mixed solvent of methanol/chloroform, the volume ratio of the eluting solution to the mixed solvent is 7:2), and removing the eluting solution by rotary evaporation to obtain an intermediate 2; the dosage ratio of the intermediate 1 to the ethylenediamine to the triethylamine to the tetrahydrofuran is 0.1mol:10.5g:50mL:200mL;
Nucleophilic substitution is carried out on the intermediate 1 and ethylenediamine, and only one amino group on the ethylenediamine participates in the reaction by controlling the molar ratio of the intermediate 1 to the ethylenediamine to be close to 1:1 and slightly excessive ethylenediamine, so that the triethylamine removes hydrogen chloride generated by the reaction and accelerates the reaction to obtain an intermediate 2; the specific reaction process is as follows:
S3, dissolving the intermediate 2 in DMF (N, N-dimethylformamide) in a three-neck flask with a stirring device, adding DCC (dicyclohexylcarbodiimide, dehydrating agent), and uniformly mixing and stirring; then slowly adding graphene oxide dispersion liquid, magnetically stirring while adding, carrying out ultrasonic treatment for 30min to uniformly disperse the graphene oxide dispersion liquid, reacting at 60 ℃ for 6h, continuously stirring during the reaction, and carrying out reduced pressure distillation, washing and freeze drying to obtain an intermediate 3; the dosage ratio of the intermediate 2 to DMF, DCC and graphene oxide dispersion liquid is 10g to 100mL to 25.8g to 200mL; the graphene oxide dispersion liquid takes DMF as a dispersion medium;
under the action of a DCC dehydrating agent, the reaction of carboxyl and amino can occur without high conditions, and the amino on the intermediate 2 is grafted onto graphene oxide to obtain an intermediate 3; the specific reaction process is as follows:
s4, uniformly mixing and stirring the intermediate 3 and methyl iodide in a three-neck flask with a stirring device, performing ultrasonic dispersion for 10min, controlling the reaction temperature at 80 ℃, reacting for 8h, performing reduced pressure distillation, washing, cooling and drying to obtain modified graphene oxide; the ratio of the dosage of the intermediate 3 to the dosage of the methyl iodide is 1g to 50mL;
Alkylation reaction is carried out on the secondary amino group on the intermediate 3 and excessive methyl iodide to obtain modified graphene oxide (quaternized product); the structure of the modified graphene oxide is shown in the following figure:
The surface of the prepared modified graphene oxide is grafted with a molecular chain through an amide group, one end of the modified graphene oxide is of a polyethylene glycol structure, polyethylene glycol is a molecular chain with extremely high hydrophilicity, and the polyethylene glycol is introduced to greatly improve the hydrophilicity of the graphene oxide, so that the compatibility with water is improved, and the modified graphene oxide can be applied to fabrics and can provide unusual antistatic performance; in addition, the organic molecular chain contains a quaternary ammonium salt structure, the quaternary ammonium salt is an excellent antibacterial structure, strong electrostatic interaction can be generated between the bacteria with positive charges and negative charges, strong adsorption can be generated on the bacteria, the permeability is good, the toxicity is low, the performance is stable, the antibacterial performance of the graphene oxide is further enhanced, and besides, the quaternary ammonium salt ion can provide certain antistatic and hydrophilic performances.
The invention has the beneficial effects that:
The graphene antibacterial slurry is prepared by dispersing modified graphene oxide and a stabilizer in deionized water, wherein the stabilizer can enable the modified graphene oxide to be uniformly and stably dispersed in the slurry, so that the antibacterial property, the ultraviolet resistance and the antistatic property of the graphene antibacterial slurry are fully exerted; the modified graphene oxide is obtained by grafting a molecular chain on the surface of the graphene oxide, and various functional groups in the molecular chain greatly improve the antibacterial property, antistatic property and hydrophilicity of the slurry; therefore, the prepared sizing agent has stable and efficient antibacterial property, hydrophilicity, and antistatic property and ultraviolet resistance to a certain extent, and has important application significance in the field of textile fabrics when being used as a finishing agent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing modified graphene oxide:
S1, uniformly mixing 12g of allyl polyoxyethylene ether (with relative molecular weight of 1200), 5mL of hydrogen peroxide and 500mL of chloroform in a three-neck flask with a stirring reflux device, controlling the reaction temperature at 60 ℃, slowly introducing 250mL of hydrogen bromide gas, carrying out reflux reaction for 4 hours, and carrying out reduced pressure distillation to remove a solvent after the reaction is finished to obtain an intermediate 1;
S2, stirring and mixing 121.1g of intermediate 1, 10.5g of ethylenediamine, 50mL of triethylamine and 200mL of tetrahydrofuran uniformly in a three-neck flask with a stirring device at room temperature under the protection of nitrogen, controlling the reaction temperature to be 75 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation, purifying by column chromatography (eluent adopts a mixed solvent of methanol/chloroform, the volume ratio of the eluent is 7:2), and removing eluent by rotary evaporation to obtain intermediate 2;
S3, dissolving 10g of the intermediate 2 in 100mL of DMF (N, N-dimethylformamide) in a three-neck flask with a stirring device, adding 25.8g of DCC (dicyclohexylcarbodiimide, dehydrating agent), and uniformly mixing and stirring; then slowly adding 200mL of graphene oxide dispersion liquid (the concentration is 1 mg/mL), magnetically stirring while adding, performing ultrasonic treatment for 30min to uniformly disperse the graphene oxide dispersion liquid, reacting for 6 hours at 60 ℃, continuously stirring during the reaction, and performing reduced pressure distillation, washing and freeze drying to obtain an intermediate 3;
s4, uniformly mixing and stirring 10g of intermediate 3 and 500mL of methyl iodide in a three-neck flask with a stirring device, performing ultrasonic dispersion for 10min, controlling the reaction temperature at 80 ℃, reacting for 8h, performing reduced pressure distillation, washing, cooling and drying to obtain the modified graphene oxide.
Example 2
Preparing modified graphene oxide:
S1, uniformly mixing 24g of allyl polyoxyethylene ether (with relative molecular weight of 1200), 10mL of hydrogen peroxide and 1000mL of chloroform in a three-neck flask with a stirring reflux device, controlling the reaction temperature at 60 ℃, slowly introducing 500mL of hydrogen bromide gas, carrying out reflux reaction for 4 hours, and carrying out reduced pressure distillation to remove a solvent after the reaction is finished to obtain an intermediate 1;
s2, stirring 242.2g of intermediate 1, 21.0g of ethylenediamine, 100mL of triethylamine and 400mL of tetrahydrofuran in a three-neck flask with a stirring device at room temperature under the protection of nitrogen, controlling the reaction temperature to be 75 ℃, reacting for 4 hours, removing part of solvent by rotary evaporation, purifying by column chromatography (eluent adopts a mixed solvent of methanol/chloroform, the volume ratio of the eluent is 7:2), and removing eluent by rotary evaporation to obtain intermediate 2;
S3, dissolving 20g of the intermediate 2 in 200mL of DMF (N, N-dimethylformamide) in a three-neck flask with a stirring device, adding 51.6g of DCC (dicyclohexylcarbodiimide, dehydrating agent), and uniformly mixing and stirring; then slowly adding 400mL of graphene oxide dispersion liquid (the concentration is 1 mg/mL), magnetically stirring while adding, performing ultrasonic treatment for 30min to uniformly disperse the graphene oxide dispersion liquid, reacting for 6 hours at 60 ℃, continuously stirring during the reaction, and performing reduced pressure distillation, washing and freeze drying to obtain an intermediate 3;
S4, uniformly mixing and stirring 20g of intermediate 3 and 1000mL of methyl iodide in a three-neck flask with a stirring device, performing ultrasonic dispersion for 10min, controlling the reaction temperature at 80 ℃, reacting for 8h, performing reduced pressure distillation, washing, cooling and drying to obtain the modified graphene oxide.
Example 3
Preparing graphene antibacterial slurry:
A1, dispersing 5g of the modified graphene oxide prepared in the embodiment 1 and 0.5g of sodium alginate in 100g of deionized water, wherein the linear speed of dispersion is 8m/s, and the dispersion is 120-160min;
And A2, performing ultra-fine treatment on the mixture obtained in the first step, wherein the pressure is 55-75MPa, and finally performing vacuum defoaming to obtain the graphene antibacterial slurry.
Example 4
Preparing graphene antibacterial slurry:
A1, dispersing 10g of the modified graphene oxide prepared in the embodiment 1 and 0.7g of hydroxyethyl cellulose in 100g of deionized water, wherein the linear speed of dispersion is 8m/s, and the dispersion is 120-160min;
And A2, performing ultra-fine treatment on the mixture obtained in the first step, wherein the pressure is 55-75MPa, and finally performing vacuum defoaming to obtain the graphene antibacterial slurry.
Example 5
Preparing graphene antibacterial slurry:
A1, dispersing 15g of the modified graphene oxide prepared in the embodiment 2 and 0.8g of sodium carboxymethyl cellulose in 100g of deionized water, wherein the linear speed of dispersion is 8m/s, and the dispersion is 120-160min;
And A2, performing ultra-fine treatment on the mixture obtained in the first step, wherein the pressure is 55-75MPa, and finally performing vacuum defoaming to obtain the graphene antibacterial slurry.
Comparative example
The modified graphene oxide in step A1 of example 5 was replaced with the same quality of graphene oxide without any treatment, and the rest of the steps were the same as example 5.
The slurries prepared in examples 3 to 5 and comparative examples were left to stand in a beaker for 15d to observe whether precipitation occurred.
The test results are shown in Table one:
List one
| Project | Example 3 | Example 4 | Example 5 | Comparative example |
| Standing for 15d | No precipitate | No precipitate | No precipitate | Obvious precipitation occurs |
The slurries prepared in examples 3-5 have good dispersibility and stability, and the modified graphene oxide is not easy to settle in the slurry.
The slurries prepared in examples 3-5 and comparative example are soaked in a fabric made of polyester fibers, and the modified polyester fiber fabric is prepared by a two-soaking and two-rolling process, dried and cooled, and is prepared into corresponding shapes to be tested according to different test standards, and the following performance tests are carried out:
evaluation of moisture absorption and quick drying Properties of textiles by national Standard GB/T21655.1-2008, section 1: the water absorption of the fabric is measured according to a single item combination test method;
The national standard GB/T20944.2-2007 (evaluation of antibacterial Properties of textiles-part 2) is adopted: the absorption method tests the bacteriostasis rate of colibacillus and staphylococcus aureus;
The ultraviolet resistance of the fabric is measured by adopting national standard GB/T18830-2009 evaluation of ultraviolet resistance of textiles;
evaluation of textile Electrostatic Properties Using national Standard GB/T12703.2-2009, section 2: the charge surface density of the fabric is measured in charge surface density;
The results are shown in Table II:
Watch II
From the second surface, the prepared sizing agent finishing fabric can endow the fabric with efficient antibacterial property, hydrophilicity and antistatic property and ultraviolet resistance to a certain extent, and has important application significance in the field of textile fabrics when being used as a finishing agent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (3)
1. The preparation method of the graphene antibacterial slurry is characterized by comprising the following steps of:
A1, dispersing modified graphene oxide and a stabilizer in deionized water, wherein the linear speed of dispersion is 8m/s, and the dispersion is 120-160min;
A2, carrying out ultra-fine treatment on the mixture obtained in the first step, wherein the pressure is 55-75MPa, and carrying out vacuum defoaming to obtain graphene antibacterial slurry;
wherein the modified graphene oxide is prepared by the following steps:
S1, mixing allyl polyoxyethylene ether, hydrogen peroxide and chloroform, controlling the reaction temperature at 60 ℃, slowly introducing hydrogen bromide gas, carrying out reflux reaction for 4 hours, and carrying out reduced pressure distillation to obtain an intermediate 1; wherein the relative molecular weight of the allyl polyoxyethylene ether is 1200; the ratio of the usage amount of the allyl polyoxyethylene ether to the usage amount of the hydrogen bromide gas is 0.1mol:0.1mol;
S2, mixing the intermediate 1, ethylenediamine, triethylamine and tetrahydrofuran at room temperature under the protection of nitrogen, reacting for 4 hours at 75 ℃, removing part of solvent by rotary evaporation, purifying by column chromatography, and removing eluent by rotary evaporation to obtain an intermediate 2; the dosage ratio of the intermediate 1 to the ethylenediamine to the triethylamine to the tetrahydrofuran is 0.1mol:10.5g:50mL:200mL;
s3, dissolving the intermediate 2 in DMF, adding DCC, mixing and stirring uniformly; then adding graphene oxide dispersion liquid, magnetically stirring while adding, performing ultrasonic treatment for 30min, reacting at 60 ℃ for 6h, stirring, performing reduced pressure distillation, washing, and freeze drying to obtain an intermediate 3; the dosage ratio of the intermediate 2 to DMF, DCC and graphene oxide dispersion liquid is 10g to 100mL to 25.8g to 200mL; the graphene oxide dispersion liquid takes DMF as a dispersion medium;
s4, mixing and stirring the intermediate 3 and methyl iodide uniformly, performing ultrasonic dispersion for 10min, controlling the reaction temperature to be 80 ℃ for reaction for 8h, performing reduced pressure distillation, washing, cooling and drying to obtain modified graphene oxide; the ratio of the amount of intermediate 3 to the amount of methyl iodide was 1 g/50 mL.
2. The preparation method of the graphene antibacterial slurry according to claim 1, wherein the mass ratio of the modified graphene oxide, the stabilizer and the deionized water in the step A1 is 5-15:0.5-0.8:100.
3. The method for preparing the graphene antibacterial slurry according to claim 1, wherein the stabilizer in the step A1 is one of sodium alginate, hydroxyethyl cellulose, sodium carboxymethyl cellulose and gelatin.
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