CN113774511A - Graphene composite polylactic acid degradable fiber and preparation method thereof - Google Patents
Graphene composite polylactic acid degradable fiber and preparation method thereof Download PDFInfo
- Publication number
- CN113774511A CN113774511A CN202111023734.8A CN202111023734A CN113774511A CN 113774511 A CN113774511 A CN 113774511A CN 202111023734 A CN202111023734 A CN 202111023734A CN 113774511 A CN113774511 A CN 113774511A
- Authority
- CN
- China
- Prior art keywords
- modifier
- polylactic acid
- graphene
- powder
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 91
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 91
- 239000000835 fiber Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 102
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920002678 cellulose Polymers 0.000 claims abstract description 43
- 239000001913 cellulose Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002074 melt spinning Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229940022769 d- lactic acid Drugs 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 229960000448 lactic acid Drugs 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 5
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 238000010521 absorption reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000209149 Zea Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 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
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229920001002 functional polymer Polymers 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
- 230000003287 optical effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000009941 weaving 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a graphene composite polylactic acid degradable fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials; step 2, mixing cellulose and a second modifier, heating and stirring, cooling, centrifugally washing, dispersing the esterified cellulose in distilled water, cooling and drying to obtain cellulose powder, mixing the cellulose powder with the first modifier, dropwise adding the second modifier for heating reaction to generate emulsion polymerization, and washing to remove impurities; step 3, adding the graphene powder and a first modifier into deionized water, stirring, heating, performing ultrasonic dispersion treatment, freeze-drying to obtain modified graphene oxide powder, then conveying the modified graphene oxide powder into a container, sealing, vacuumizing, and filling nitrogen for protection; and 4, melting and mixing the modified graphene powder, the modified cellulose powder and the polylactic acid slices, and spinning into bundles. The invention also provides the graphene composite polylactic acid degradable fiber prepared by the method. The composite fiber prepared by the invention has the functions of antibiosis, cool feeling and the like.
Description
Technical Field
The invention relates to a graphene composite fiber in the technical field of novel functional polymer materials and a preparation method thereof, and particularly relates to a graphene composite polylactic acid degradable fiber 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.
Polylactic acid fiber (PLA) is produced from corn starch, so the fiber is also called corn fiber, and the product obtained by using the polylactic acid as a raw material has good biocompatibility and biological absorbability, antibacterial property and flame resistance, and the PLA has the best heat resistance in degradable thermoplastic polymer materials. However, polylactic acid fibers have poor water absorption and are easy to cause static electricity, which results in poor subsequent weaving, dyeing and wearing comfort, so that it is necessary to develop a graphene composite polylactic acid degradable fiber which has good moisture absorption and excellent antibacterial and far infrared functions.
Disclosure of Invention
The invention aims to provide a graphene composite fiber and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a graphene composite polylactic acid degradable fiber, wherein the method comprises: step 1, weighing raw materials in proportion; step 2, cellulose modification preparation: mixing cellulose and a second modifier, stirring under a heating condition, cooling the mixture to room temperature after the reaction is finished, centrifugally washing, dispersing the esterified cellulose in distilled water, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dropwise adding the second modifier, heating for reaction, carrying out emulsion polymerization, and washing to remove impurities to obtain esterified modified cellulose powder; step 3, preparing modified graphene powder: adding graphene powder and a first modifier into deionized water, stirring, heating, performing ultrasonic dispersion treatment to obtain modified graphene slurry, freeze-drying to obtain modified graphene oxide powder, feeding the powder into a container, sealing, vacuumizing, and filling nitrogen for protection; step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles to obtain the modified graphene composite polylactic acid degradable fiber.
In the step 1, the raw materials include, by mass, 80-99% of polylactic acid, 0.1-15% of graphene, 0.1-1% of a first modifier, 0.1-1% of a second modifier, and 0.1-10% of cellulose.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the following steps of preparing graphene by a mechanical stripping method, a chemical vapor deposition method and an oxidation-reduction method, wherein the graphene is prepared by any one or more of the mechanical stripping method, the chemical vapor deposition method and the oxidation-reduction method.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the step of preparing a graphene composite polylactic acid degradable fiber, wherein the polylactic acid is a slice and contains any one or more of poly-d-lactic acid, poly-L-lactic acid and poly-dL-lactic acid.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the step of preparing the graphene composite polylactic acid degradable fiber, wherein the first modifier comprises one or more of polyethylene glycol, sodium dodecyl sulfate and polyvinylpyrrolidone.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the step of preparing the graphene composite polylactic acid degradable fiber, wherein the second modifier comprises one or more of octadecylamine, potassium persulfate, butyl acrylate, methyl acrylate, tetrabutylammonium acetate and N, N-dimethylacetamide.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the following steps of in step 2, mixing cellulose and a second modifier, wherein the amount of the second modifier accounts for 50-80% of the total amount of the second modifier in percentage by mass, stirring and reacting at 50-70 ℃ for 30-60 min, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water in a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, wherein the amount of the first modifier accounts for 20-40% of the total amount of the first modifier in percentage by mass, gradually dropwise adding the rest of the second modifier, heating to react, carrying out emulsion polymerization, and washing to remove impurities to obtain the esterified modified cellulose powder.
In the step 3, the graphene powder and the rest of the first modifier are added into deionized water to enable the concentration of graphene to be 1-10 mg/ml, the mixture is stirred for 20-50 min, the temperature is increased to 50-80 ℃, and then ultrasonic dispersion treatment is carried out for 30-50 min to obtain the modified graphene slurry.
The preparation method of the graphene composite polylactic acid degradable fiber comprises the step 4 of melt spinning, wherein the spinning temperature is 200-210 ℃, and the spinning speed is 500-2000 m/min.
The invention also provides the graphene composite polylactic acid degradable fiber prepared by the method.
The graphene composite polylactic acid degradable fiber and the preparation method thereof provided by the invention have the following advantages:
the melting method graphene composite polylactic acid fiber has excellent effects of antibiosis, far infrared and the like, wherein the bacteriostasis rates of escherichia coli, staphylococcus aureus and candida albicans reach 99.9%, the far infrared temperature rise reaches 0.88, and the functionality is good. Meanwhile, the modified polylactic acid fiber has greatly improved hydrophilicity, and the fabric prepared from the polylactic acid fiber is easy to dye and more comfortable to use. And the fiber can be degraded under natural conditions after use, so that the environment is protected.
The fusion-method modified graphene composite polylactic acid fiber prepared by the method has the advantages of simple process, easy operation, low cost and high economic benefit, and is suitable for large-scale industrial production.
Detailed Description
The following further describes embodiments of the present invention.
The invention provides a preparation method of a graphene composite polylactic acid degradable fiber, which comprises the following steps:
step 1, weighing raw materials in proportion; step 2, cellulose modification preparation: mixing cellulose and a second modifier, stirring under a heating condition, cooling the mixture to room temperature after the reaction is finished, centrifugally washing, dispersing the esterified cellulose in distilled water, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dropwise adding the second modifier, heating for reaction, carrying out emulsion polymerization, and washing to remove impurities to obtain esterified modified cellulose powder; step 3, preparing modified graphene powder: adding graphene powder and a first modifier into deionized water, stirring, heating, performing ultrasonic dispersion treatment to obtain modified graphene slurry, freeze-drying to obtain modified graphene oxide powder, feeding the powder into a container, sealing, vacuumizing, and filling nitrogen for protection; step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles to obtain the modified graphene composite polylactic acid degradable fiber.
Preferably, in the step 1, the raw materials comprise, by mass, 80% -99% of polylactic acid, 0.1% -15% of graphene, 0.1% -1% of a first modifier, 0.1% -1% of a second modifier, and 0.1% -10% of cellulose.
The graphene is prepared by any one or more of a mechanical stripping method, a chemical vapor deposition method, a redox method and the like.
The polylactic acid is a section, and comprises one or more of poly d-lactic acid (PDLA), poly L-lactic acid (PLLA) and poly dL-lactic acid (PDLLA).
The first modifier comprises any one or more of polyethylene glycol, sodium dodecyl sulfate, polyvinylpyrrolidone (PVP) and the like.
The second modifier comprises any one or more of octadecylamine, potassium persulfate, butyl acrylate, methyl acrylate, tetrabutylammonium acetate, N-dimethylacetamide, and the like.
In the step 2, firstly mixing cellulose and a second modifier, wherein the amount of the second modifier is 50-80% of the total amount of the second modifier in percentage by mass, stirring and reacting at 50-70 ℃ for 30-60 min, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, wherein the amount of the first modifier is 20-40% of the total amount of the first modifier in percentage by mass, gradually dripping the remaining second modifier for heating reaction to generate emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
In the step 3, adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 1-10 mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry.
And 4, performing melt spinning in the step 4, wherein the spinning temperature is 200-210 ℃, and the spinning speed is 500-2000 m/min.
The invention also provides the graphene composite polylactic acid degradable fiber prepared by the method.
The graphene composite polylactic acid degradable fiber and the preparation method thereof provided by the invention are further described below with reference to the embodiments.
Example 1
A preparation method of a graphene composite polylactic acid degradable fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Preferably, each raw material comprises 99% of polylactic acid, 0.1% of graphene, 0.1% of first modifier, 0.1% of second modifier and 0.7% of cellulose in percentage by mass.
The graphene is prepared by a mechanical stripping method. The polylactic acid is a slice and comprises poly-d-lactic acid. The first modifier comprises polyethylene glycol. The second modifier comprises octadecylamine.
And 2, modifying and preparing the cellulose.
Firstly, mixing cellulose and a second modifier, wherein the dosage of the second modifier is 50 percent of the total amount of the second modifier according to the mass percentage; stirring and reacting for 30-60 min at 50-70 ℃, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dripping the rest second modifier into the mixture according to the mass percentage to perform heating reaction, performing emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
And 3, preparing modified graphene powder.
Adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 1mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry. And then freeze-drying to obtain modified graphene oxide powder, then conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection.
Step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles at the spinning temperature of 200-2000 m/min and the spinning speed of 500-2000m/min to obtain the modified graphene composite polylactic acid degradable fiber.
The embodiment also provides the graphene composite polylactic acid degradable fiber prepared by the method.
Example 2
A preparation method of a graphene composite polylactic acid degradable fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Preferably, each raw material comprises, by mass, 84% of polylactic acid, 5% of graphene, 0.5% of a first modifier, 0.5% of a second modifier and 10% of cellulose.
The graphene is prepared by a chemical vapor deposition method. The polylactic acid is a slice and comprises poly L-lactic acid. The first modifier comprises sodium dodecyl sulfate. The second modifier comprises potassium persulfate.
And 2, modifying and preparing the cellulose.
Firstly, mixing cellulose and a second modifier, wherein the using amount of the second modifier is 58 percent of the total amount of the second modifier according to the mass percentage; stirring and reacting for 30-60 min at 50-70 ℃, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dripping the rest second modifier into the mixture, heating for reaction, carrying out emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
And 3, preparing modified graphene powder.
Adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 3mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry. And then freeze-drying to obtain modified graphene oxide powder, then conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection.
Step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles at the spinning temperature of 200-2000 m/min and the spinning speed of 500-2000m/min to obtain the modified graphene composite polylactic acid degradable fiber.
The embodiment also provides the graphene composite polylactic acid degradable fiber prepared by the method.
Example 3
A preparation method of a graphene composite polylactic acid degradable fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Preferably, each raw material comprises, by mass, 84.3% of polylactic acid, 10% of graphene, 0.3% of a first modifier, 0.4% of a second modifier and 5% of cellulose.
The graphene is prepared by an oxidation-reduction method. The polylactic acid is a slice and comprises poly dL-lactic acid. The first modifier comprises polyvinylpyrrolidone.
The second modifier comprises butyl acrylate or methyl acrylate.
And 2, modifying and preparing the cellulose.
Firstly, mixing cellulose and a second modifier, wherein the using amount of the second modifier is 65 percent of the total amount of the second modifier according to the mass percentage; stirring and reacting for 30-60 min at 50-70 ℃, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dripping the rest second modifier into the mixture according to the mass percentage, heating for reaction, carrying out emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
And 3, preparing modified graphene powder.
Adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 5mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry. And then freeze-drying to obtain modified graphene oxide powder, then conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection.
Step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles at the spinning temperature of 200-2000 m/min and the spinning speed of 500-2000m/min to obtain the modified graphene composite polylactic acid degradable fiber.
The embodiment also provides the graphene composite polylactic acid degradable fiber prepared by the method.
Example 4
A preparation method of a graphene composite polylactic acid degradable fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Preferably, each raw material comprises, by mass, 86.5% of polylactic acid, 12% of graphene, 0.6% of a first modifier, 0.8% of a second modifier and 0.1% of cellulose.
The graphene is prepared by a mechanical stripping method and a chemical vapor deposition method.
The polylactic acid is a slice, and comprises poly-d-lactic acid and poly-L-lactic acid.
The first modifier comprises polyethylene glycol, sodium dodecyl sulfate and polyvinylpyrrolidone.
The second modifier comprises tetrabutylammonium acetate, N-dimethylacetamide.
And 2, modifying and preparing the cellulose.
Firstly, mixing cellulose and a second modifier, wherein the using amount of the second modifier is 70 percent of the total amount of the second modifier in percentage by mass; stirring and reacting for 30-60 min at 50-70 ℃, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dripping the rest second modifier into the mixture, heating for reaction, carrying out emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
And 3, preparing modified graphene powder.
Adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 8mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry. And then freeze-drying to obtain modified graphene oxide powder, then conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection.
Step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles at the spinning temperature of 200-2000 m/min and the spinning speed of 500-2000m/min to obtain the modified graphene composite polylactic acid degradable fiber.
The embodiment also provides the graphene composite polylactic acid degradable fiber prepared by the method.
Example 5
A preparation method of a graphene composite polylactic acid degradable fiber comprises the following steps:
step 1, weighing the raw materials in proportion.
Preferably, each raw material comprises, by mass, 80% of polylactic acid, 15% of graphene, 1% of a first modifier, 1% of a second modifier and 3% of cellulose.
The graphene is prepared by any one or more of a mechanical stripping method, a chemical vapor deposition method and a redox method.
The polylactic acid is a slice and comprises any one or more of poly-d-lactic acid, poly-L-lactic acid and poly-dL-lactic acid.
The first modifier comprises any one or more of polyethylene glycol, sodium dodecyl sulfate and polyvinylpyrrolidone.
The second modifier comprises any one or more of octadecylamine, potassium persulfate, butyl acrylate, methyl acrylate, tetrabutylammonium acetate and N, N-dimethylacetamide.
And 2, modifying and preparing the cellulose.
Firstly, mixing cellulose and a second modifier, wherein the using amount of the second modifier is 80 percent of the total amount of the second modifier in percentage by mass; stirring and reacting for 30-60 min at 50-70 ℃, cooling the mixture to room temperature after the reaction is finished, centrifugally washing for 3-5 times, dispersing the esterified cellulose in distilled water by using a solvent replacement mode, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dripping the rest second modifier into the mixture, heating for reaction to generate emulsion polymerization, washing and removing impurities to obtain the esterified modified cellulose powder.
And 3, preparing modified graphene powder.
Adding the graphene powder and the rest of the first modifier into deionized water to enable the concentration of graphene to be 10mg/ml, stirring for 20-50 min, raising the temperature to 50-80 ℃, and performing ultrasonic dispersion treatment for 30-50 min to obtain modified graphene slurry. And then freeze-drying to obtain modified graphene oxide powder, then conveying the powder into a container, sealing, vacuumizing, and then filling nitrogen for protection.
Step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles at the spinning temperature of 200-2000 m/min and the spinning speed of 500-2000m/min to obtain the modified graphene composite polylactic acid degradable fiber.
The embodiment also provides the graphene composite polylactic acid degradable fiber prepared by the method.
The graphene composite polylactic acid degradable fiber prepared by each embodiment of the invention is tested, and the results are shown in table 1 below.
Table 1 test results.
The invention provides a graphene composite polylactic acid degradable fiber and a preparation method thereof, aiming at preparing a modified graphene polylactic acid composite fiber by utilizing a modified graphene dispersion system, a nano-cellulose modification technology and a polylactic acid melting method technology, wherein the composite fiber has excellent antibacterial and far infrared characteristics, and meanwhile, the modified nano-cellulose is added into the polylactic acid fiber, so that the hydrophilicity of the polylactic acid fiber is greatly improved, and the modified cellulose and polylactic acid have better compatibility, so that the fiber strength of the prepared graphene modified polylactic acid composite fiber is greatly improved while the better hydrophilicity is maintained. The graphene in the composite fiber prepared by the invention is uniformly dispersed, is not easy to fall off, and has durability in functionality.
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. A preparation method of a graphene composite polylactic acid degradable fiber is characterized by comprising the following steps:
step 1, weighing raw materials in proportion;
step 2, cellulose modification preparation: mixing cellulose and a second modifier, stirring under a heating condition, cooling the mixture to room temperature after the reaction is finished, centrifugally washing, dispersing the esterified cellulose in distilled water, cooling and drying to obtain cellulose powder, mixing the cellulose powder with a first modifier, gradually dropwise adding the second modifier, heating for reaction, carrying out emulsion polymerization, and washing to remove impurities to obtain esterified modified cellulose powder;
step 3, preparing modified graphene powder: adding graphene powder and a first modifier into deionized water, stirring, heating, performing ultrasonic dispersion treatment to obtain modified graphene slurry, freeze-drying to obtain modified graphene oxide powder, feeding the powder into a container, sealing, vacuumizing, and filling nitrogen for protection;
step 4, melt spinning: and (3) adding the modified graphene powder obtained in the step (3), the modified cellulose powder obtained in the step (2) and the polylactic acid slices into a screw extruder for melt mixing, filtering by a spinning manifold, and spinning into bundles to obtain the modified graphene composite polylactic acid degradable fiber.
2. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 1, wherein in the step 1, each raw material comprises, by mass, 80% -99% of polylactic acid, 0.1% -15% of graphene, 0.1% -1% of a first modifier, 0.1% -1% of a second modifier, and 0.1% -10% of cellulose.
3. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 2, wherein the graphene is prepared by any one or more of a mechanical stripping method, a chemical vapor deposition method and a redox method.
4. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 2, wherein the polylactic acid is a slice and comprises any one or more of poly-d-lactic acid, poly-L-lactic acid and poly-dL-lactic acid.
5. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 2, wherein the first modifier comprises one or more of polyethylene glycol, sodium dodecyl sulfate and polyvinylpyrrolidone.
6. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 2, wherein the second modifier comprises one or more of octadecylamine, potassium persulfate, butyl acrylate, methyl acrylate, tetrabutylammonium acetate and N, N-dimethylacetamide.
7. The method for preparing the graphene composite polylactic acid degradable fiber according to claim 1, in the step 2, the cellulose and the second modifier are mixed, the dosage of the second modifier is 50 to 80 percent of the total amount of the second modifier according to the mass percentage, stirring at 50-70 deg.C for reaction for 30-60 min, cooling the mixture to room temperature after reaction, centrifuging and washing for 3-5 times, dispersing esterified cellulose in distilled water by solvent replacement, cooling and drying to obtain cellulose powder, and then mixing the esterified modified cellulose powder with a first modifier, wherein the dosage of the first modifier is 20-40% of the total amount of the first modifier according to the mass percentage, gradually dropwise adding the rest second modifier for heating reaction to generate emulsion polymerization, and washing to remove impurities to obtain the esterified modified cellulose powder.
8. The preparation method of the graphene composite polylactic acid degradable fiber according to claim 1, wherein in the step 3, the graphene powder and the rest of the first modifier are added into deionized water, the concentration of graphene is 1-10 mg/ml, the mixture is stirred for 20-50 min, the temperature is raised to 50-80 ℃, and then ultrasonic dispersion treatment is carried out for 30-50 min, so as to obtain the modified graphene slurry.
9. The method for preparing the graphene composite polylactic acid degradable fiber as claimed in claim 1, wherein the melt spinning in the step 4 is carried out at a spinning temperature of 200-210 ℃ and a spinning speed of 500-2000 m/min.
10. The graphene composite polylactic acid degradable fiber prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111023734.8A CN113774511A (en) | 2021-09-02 | 2021-09-02 | Graphene composite polylactic acid degradable fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111023734.8A CN113774511A (en) | 2021-09-02 | 2021-09-02 | Graphene composite polylactic acid degradable fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113774511A true CN113774511A (en) | 2021-12-10 |
Family
ID=78840698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111023734.8A Pending CN113774511A (en) | 2021-09-02 | 2021-09-02 | Graphene composite polylactic acid degradable fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113774511A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193318A (en) * | 2017-12-28 | 2018-06-22 | 上海德福伦化纤有限公司 | A kind of graphene modified polylactic acid fiber and preparation method thereof |
| CN108842221A (en) * | 2018-07-12 | 2018-11-20 | 山东联星能源集团有限公司 | A kind of ultrahigh-strength graphene modified fiber materials and preparation method thereof |
| CN109487352A (en) * | 2018-11-27 | 2019-03-19 | 杭州三信实业有限公司 | Graphene polylactic acid bicomponent composite fibre and preparation method thereof and equipment |
| CN111235671A (en) * | 2020-02-11 | 2020-06-05 | 任国峰 | Modified graphene anti-ultraviolet polyamide fiber and preparation method thereof |
| CN113005555A (en) * | 2021-03-10 | 2021-06-22 | 南通强生石墨烯科技有限公司 | Graphene luminous chinlon composite fiber and preparation method thereof |
-
2021
- 2021-09-02 CN CN202111023734.8A patent/CN113774511A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193318A (en) * | 2017-12-28 | 2018-06-22 | 上海德福伦化纤有限公司 | A kind of graphene modified polylactic acid fiber and preparation method thereof |
| CN108842221A (en) * | 2018-07-12 | 2018-11-20 | 山东联星能源集团有限公司 | A kind of ultrahigh-strength graphene modified fiber materials and preparation method thereof |
| CN109487352A (en) * | 2018-11-27 | 2019-03-19 | 杭州三信实业有限公司 | Graphene polylactic acid bicomponent composite fibre and preparation method thereof and equipment |
| CN111235671A (en) * | 2020-02-11 | 2020-06-05 | 任国峰 | Modified graphene anti-ultraviolet polyamide fiber and preparation method thereof |
| CN113005555A (en) * | 2021-03-10 | 2021-06-22 | 南通强生石墨烯科技有限公司 | Graphene luminous chinlon composite fiber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yadav et al. | Cellulose nanocrystals reinforced κ-carrageenan based UV resistant transparent bionanocomposite films for sustainable packaging applications | |
| Swaroop et al. | Development of blown polylactic acid-MgO nanocomposite films for food packaging | |
| Jiang et al. | Preparation and characterization of natural corn starch-based composite films reinforced by eggshell powder | |
| Sheng et al. | High-toughness PLA/Bamboo cellulose nanowhiskers bionanocomposite strengthened with silylated ultrafine bamboo-char | |
| Li et al. | Preparation of polylactic acid/TEMPO-oxidized bacterial cellulose nanocomposites for 3D printing via Pickering emulsion approach | |
| Ambrosio-Martín et al. | Melt polycondensation to improve the dispersion of bacterial cellulose into polylactide via melt compounding: enhanced barrier and mechanical properties | |
| Rajisha et al. | Preparation and characterization of potato starch nanocrystal reinforced natural rubber nanocomposites | |
| CN111235671A (en) | Modified graphene anti-ultraviolet polyamide fiber and preparation method thereof | |
| Gironès et al. | Natural fiber-reinforced thermoplastic starch composites obtained by melt processing | |
| Lee et al. | Preparation of cellulose nanowhiskers and their reinforcing effect in polylactide | |
| Ketabchi et al. | Mechanical and thermal properties of polylactic acid composites reinforced with cellulose nanoparticles extracted from kenaf fibre | |
| Tsou et al. | The preparation and performance of poly (butylene adipate) terephthalate/corn stalk composites | |
| Shi et al. | Preparation, characterization, and biodegradation of poly (butylene succinate)/cellulose triacetate blends | |
| Zhang et al. | Preparation and properties of poly (lactic acid)/sesbania gum/nano-TiO 2 composites | |
| CN113005555A (en) | Graphene luminous chinlon composite fiber and preparation method thereof | |
| Ma et al. | Mechanical, thermal, and morphological properties of PLA biocomposites toughened with silylated bamboo cellulose nanowhiskers | |
| Barghini et al. | Poly‐(ε‐caprolactone)(PCL) and poly (hydroxy‐butyrate)(PHB) blends containing seaweed fibers: Morphology and thermal‐mechanical properties | |
| Medeiros et al. | Synthesis, Characterization and Nanocomposite Formation of Poly (glycerol succinate-co-maleate) with Nanocrystalline Cellulose | |
| Rodrigues et al. | Preparation and characterization of polymeric films based on PLA, PBAT and corn starch and babassu mesocarp starch by flat extrusion | |
| Panitchakarn et al. | Synthesis and characterization of natural rubber/coal fly ash composites via latex aqueous microdispersion | |
| Sepúlveda et al. | Poly (lactic acid)/D‐limonene/ZnO bio‐nanocomposites with antimicrobial properties | |
| CN106133032B (en) | Method for incorporating wet natural fibers and starch into thermoplastics | |
| CN114524959B (en) | Ceramic nanocellulose reinforced full-biodegradable material composite membrane and preparation method thereof | |
| CN109233230A (en) | A kind of hybrid polydactyl acid membrane material and preparation method thereof | |
| Xu et al. | Interface self‐reinforcing ability and antibacterial effect of natural chitosan modified polyvinyl chloride‐based wood flour composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211210 |