CN115262029B - Graphene polyamide filament and spinning method thereof - Google Patents
Graphene polyamide filament and spinning method thereof Download PDFInfo
- Publication number
- CN115262029B CN115262029B CN202210853556.XA CN202210853556A CN115262029B CN 115262029 B CN115262029 B CN 115262029B CN 202210853556 A CN202210853556 A CN 202210853556A CN 115262029 B CN115262029 B CN 115262029B
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyamide resin
- agent
- sample
- polyamide
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- 239000004952 Polyamide Substances 0.000 title claims abstract description 43
- 229920002647 polyamide Polymers 0.000 title claims abstract description 43
- 238000009987 spinning Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 10
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 62
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 239000000017 hydrogel Substances 0.000 claims abstract description 21
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 16
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 16
- 241001330002 Bambuseae Species 0.000 claims abstract description 16
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 16
- 239000011425 bamboo Substances 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 16
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 7
- 229960003371 protocatechualdehyde Drugs 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000004804 winding Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000002135 nanosheet Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 241001589086 Bellapiscis medius Species 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002381 microspectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/04—Melting filament-forming substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/106—Filtering
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
-
- 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
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a novel graphene polyamide filament and a spinning method thereof, and in particular relates to the technical field of graphene polyamide filaments, which comprises the following raw materials: polyamide resin, maleic anhydride, grafting agent, cross-linking agent, bamboo fiber, modified antibacterial agent, graphene hydrogel and organic solvent. According to the invention, the grafting agent neoprene adhesive and the cross-linking agent protocatechuic aldehyde are used for primarily modifying the polyamide resin, so that the molecular branching degree of the polyamide resin is improved, the intermolecular hydrogen bonds are weakened, the flexibility of the polyamide resin is further improved, and meanwhile, the modified polyamide resin plays a coupling role by adding maleic anhydride into the modified polyamide resin, so that the tensile strength and impact strength of the modified polyamide resin are further improved, the polarity of the antibacterial agent and the interface effect of the internal interface are improved by modifying the antibacterial agent, and the antibacterial property of the polyamide resin and the insulation property of the polyamide resin are greatly improved.
Description
Technical Field
The invention relates to the technical field of graphene polyamide filaments, in particular to a novel graphene polyamide filament and a spinning method thereof.
Background
The polyamide resin is a polycondensation type polymer compound having a-CONH structure in the molecule, and is usually obtained by polycondensation of a dibasic acid and a diamine. The most prominent advantage of polyamide resins is the particularly narrow range of softening points, unlike other thermoplastic resins which have a gradual curing or softening process which causes rapid curing when the temperature is slightly below the melting point. Polyamide commonly known as Nylon (Nylon), PA for short, with a density of 1.15g/cm 3 Is that the molecule main chain contains repeated amide group- [ NHCO]Thermoplastic resins are generally referred to as including aliphatic PA, aliphatic-aromatic PA and aromatic PA.
Graphene is a kind of graphene with sp 2 New materials with hybridized linked carbon atoms closely packed into a monolayer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, and has important application prospects in the aspects of material science, micro-nano processing, energy, biomedicine, drug delivery and the like.
However, the existing graphene polyamide filaments have poor durability, toughness is rapidly reduced after long-term use and washing, and antibacterial property is greatly reduced with the increase of the use time, so that a novel graphene polyamide filament is urgently needed to solve the problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a novel graphene polyamide filament and a spinning method thereof, and the problems to be solved by the invention are as follows: how to improve the toughness and the antibacterial property of the graphene polyamide filaments.
In order to achieve the above purpose, the present invention provides the following technical solutions: the novel graphene polyamide filament comprises the following raw materials in percentage by weight: 20-30% of polyamide resin, 10-15% of maleic anhydride, 12-16% of grafting agent, 14-17% of cross-linking agent, 9-12% of bamboo fiber, 16-24% of modified antibacterial agent, 7-10% of graphene, 4-7% of graphene hydrogel and 3-6% of organic solvent.
In a preferred embodiment: 22-28% of polyamide resin, 12-14% of maleic anhydride, 13-15% of grafting agent, 15-16% of cross-linking agent, 10-11% of bamboo fiber, 18-20% of modified antibacterial agent, 8-9% of graphene, 5-6% of graphene hydrogel and 4-5% of organic solvent.
In a preferred embodiment: 25% of polyamide resin, 12.5% of maleic anhydride, 14% of grafting agent, 15.5% of cross-linking agent, 10.5% of bamboo fiber, 20% of modified antibacterial agent, 8.5% of graphene, 5.5% of graphene hydrogel and 4.5% of organic solvent.
In a preferred embodiment: the grafting agent is neoprene adhesive (company: shanghai micro-spectrum detection technology group Co., ltd.), the crosslinking agent is protocatechuic aldehyde (CAS number: 139-85-5), the antibacterial agent is nano silver antibacterial agent (company: hubei Cheng Feng chemical Co., ltd.), and the organic solvent is one of n-butanol (CAS number: 71-36-3) or terpineol (CAS number: 8000-41-7).
The spinning method of the novel graphene polyamide filament comprises the following specific preparation steps:
step one: firstly, weighing polyamide resin, adding the polyamide resin into a reaction bottle, adding a grafting agent into the reaction bottle, then enabling the polyamide resin in the reaction bottle to react with the grafting agent for a certain time, vacuumizing the reaction bottle after the reaction is completed, standing to obtain a sample A, adding a cross-linking agent into the sample A, performing normal pressure reaction for a certain time, and then performing reduced pressure reaction to obtain modified polyamide resin;
step two: weighing polyethylene glycol (CAS number: 25322-68-3), adding into a reactor, heating to a molten state, stirring and mixing uniformly, adding graphene oxide nanosheets (company: siami Biotechnology Co., ltd.), adding maleic anhydride into the reactor, refluxing, introducing dry air into the reactor, bubbling for a certain time, discharging unreacted maleic anhydride to obtain a sample B, weighing bamboo fibers, the sample B and the modified polyamide resin obtained in the step one, stirring and mixing to obtain a mixture;
step three: weighing silver nitrate (CAS number: 7761-88-8), placing into a mixing bottle, adding water into the mixing bottle to obtain water solution, slowly adding cysteine (CAS number: 17817-88-8) water solution into the water solution, stirring with an electric stirring device to obtain sample C, adding tris (CAS number: 77-86-1) and NaBH into the sample C 4 Stirring and mixing the solution (company: shanghai Kaijin chemical engineering Co., ltd.), adding glacial acetic acid (CAS number: 76-49-3) for reaction, filtering the solution to obtain precipitate, and washing the precipitate with deionized water to obtain the modified antibacterial agent;
step four: weighing the mixture obtained in the second step and the modified antibacterial agent obtained in the third step, melting, filtering the melted material, and adding graphene, graphene hydrogel and an organic solvent into the filtered material, and stirring and mixing to obtain a sample D;
step five: spinning the sample D obtained in the step four, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step six: and D, treating the pre-oriented yarn obtained in the step five through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the novel graphene polyamide filament.
In a preferred embodiment: the standing time in the first step is (2-3) h, and the pressure after decompression in the first step is (0.07-0.1) MPa.
In a preferred embodiment: the weight ratio of polyethylene glycol, graphene oxide nano-sheets and maleic anhydride in the second step is (0.4-0.6): (0.5-0.7): 1, wherein the stirring rate in the second step is 500-600r/min, the bubbling time in the second step is (1-2) h, and the reflux time in the second step is (3-5) h.
In a preferred embodiment: silver nitrate, water, cysteine aqueous solution, tris (hydroxymethyl) aminomethane and NaBH in the third step 4 The weight ratio of the solution to glacial acetic acid to deionized water is 1: (0.3-0.5): (0.5-0.8): (0.4-0.6): (0.5-0.7): (0.4-0.5): (0.2-0.4), wherein the electric stirring speed in the third step is 700-900r/min.
In a preferred embodiment: the electric stirring time in the third step is (1-3) h, and the flushing time in the third step is (2-3) h.
In a preferred embodiment: the electric stirrer in the third step is an electromagnetic stirrer, and the spinning in the fifth step is cooled by water cooling.
The invention has the technical effects and advantages that:
1. the novel graphene polyamide filament prepared by adopting the raw material formula disclosed by the invention has the advantages that the grafting agent neoprene adhesive and the cross-linking agent protocatechualdehyde are used for primarily modifying the polyamide resin, so that the molecular branching degree of the polyamide resin is improved, the intermolecular hydrogen bonds are weakened, the flexibility of the polyamide resin is further increased, and meanwhile, the modified polyamide resin can be subjected to the combination of chemical bonds and hydrogen bonds through the maleic anhydride added into the modified polyamide resin, so that the coupling effect is achieved, the bonding strength of a two-phase interface is improved, and the tensile strength and the impact strength of the modified polyamide resin are greatly improved;
2. according to the invention, the polarity of the antibacterial agent and the interface effect of the internal interface are improved through modification of the antibacterial agent, the aggregation of the metal nano powder is reduced, the polarity of the surface of the antibacterial agent is reduced, the compatibility between the metal nano powder and the polyamide resin matrix is improved, the antibacterial property of the polyamide resin and the insulativity of the polyamide resin are greatly improved, the graphene hydrogel is added to rapidly act on the wound of a patient, and the hydrogel rapidly solidifies and treats the blood of the wound, so that the sterilization and hemostasis performances of the graphene-polyamide composite material are further enhanced, and the drug effect is more durable.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
The novel graphene polyamide filament of the embodiment comprises the following raw materials in percentage by weight: 20% of polyamide resin, 10% of maleic anhydride, 12% of grafting agent, 14% of cross-linking agent, 9% of bamboo fiber, 16% of modified antibacterial agent, 7% of graphene, 4% of graphene hydrogel and 3% of organic solvent.
The grafting agent is neoprene adhesive, the cross-linking agent is protocatechuic aldehyde (CAS number: 139-85-5), the antibacterial agent is nano silver antibacterial agent (company: hubei Chengfeng chemical Co., ltd.), and the organic solvent is n-butanol (CAS number: 71-36-3).
The preparation method comprises the following specific steps:
step one: firstly, weighing polyamide resin, adding the polyamide resin into a reaction bottle, adding a grafting agent into the reaction bottle, then enabling the polyamide resin in the reaction bottle to react with the grafting agent for a certain time, vacuumizing the reaction bottle after the reaction is completed, standing to obtain a sample A, adding a cross-linking agent into the sample A, performing normal pressure reaction for a certain time, and then performing reduced pressure reaction to obtain modified polyamide resin;
step two: weighing polyethylene glycol (CAS number: 25322-68-3), adding into a reactor, heating to a molten state, stirring and mixing uniformly, adding graphene oxide nanosheets (company: siami Biotechnology Co., ltd.), adding maleic anhydride into the reactor, refluxing, introducing dry air into the reactor, bubbling for a certain time, discharging unreacted maleic anhydride to obtain a sample B, weighing bamboo fibers, the sample B and the modified polyamide resin obtained in the step one, stirring and mixing to obtain a mixture;
step three: weighing silver nitrate (CAS number: 7761-88-8), placing into a mixing bottle, adding water into the mixing bottle to obtain water solution, slowly adding cysteine (CAS number: 17817-88-8) water solution into the water solution, stirring with an electric stirring device to obtain sample C, adding tris (CAS number: 77-86-1) and NaBH into the sample C 4 Stirring and mixing the solution (company: shanghai Kaijin chemical engineering Co., ltd.), adding glacial acetic acid (CAS number: 76-49-3) for reaction, filtering the solution to obtain precipitate, and washing the precipitate with deionized water to obtain the modified antibacterial agent;
step four: weighing the mixture obtained in the second step and the modified antibacterial agent obtained in the third step, melting, filtering the melted material, and adding graphene, graphene hydrogel and an organic solvent into the filtered material, and stirring and mixing to obtain a sample D;
step five: spinning the sample D obtained in the step four, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step six: and D, treating the pre-oriented yarn obtained in the step five through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the novel graphene polyamide filament.
Wherein the standing time in the first step is 2h, and the pressure after decompression is 0.07MPa.
The weight ratio of polyethylene glycol, graphene oxide nano-sheets and maleic anhydride in the second step is 0.4:0.5:1, stirring rate of 600r/min, bubbling time of 2h, and reflux time of 3h.
Silver nitrate, water, cysteine aqueous solution, tris (hydroxymethyl) aminomethane and NaBH in the third step 4 The weight ratio of the solution to glacial acetic acid to deionized water is 1:0.3:0.5:0.4:0.5:0.4:0.2, the electric stirring speed is 900r/min, the electric stirring time is 1h, and the flushing time is 2h. The electric stirrer is an electromagnetic stirrer, and the spinning in the fifth step is cooled by water cooling.
Example 2
Unlike example 1, the novel graphene polyamide filaments comprise the following raw materials in weight percent: 25% of polyamide resin, 12.5% of maleic anhydride, 14% of grafting agent, 15.5% of cross-linking agent, 10.5% of bamboo fiber, 20% of modified antibacterial agent, 8.5% of graphene, 5.5% of graphene hydrogel and 4.5% of organic solvent.
Example 3
Unlike examples 1 and 2, the novel graphene polyamide filaments comprise the following raw materials in weight percent: 30% of polyamide resin, 15% of maleic anhydride, 16% of grafting agent, 17% of cross-linking agent, 12% of bamboo fiber, 24% of modified antibacterial agent, 10% of graphene, 7% of graphene hydrogel and 6% of organic solvent.
Example 4
The novel graphene polyamide filament comprises the following raw materials in percentage by weight: 20% of polyamide resin, 10% of maleic anhydride, 12% of grafting agent, 14% of cross-linking agent, 9% of bamboo fiber, 16% of antibacterial agent, 7% of graphene, 4% of graphene hydrogel and 3% of organic solvent.
The grafting agent is neoprene adhesive, the cross-linking agent is protocatechuic aldehyde (CAS number: 139-85-5), the antibacterial agent is nano silver antibacterial agent (company: hubei Chengfeng chemical Co., ltd.), and the organic solvent is terpineol (CAS number: 8000-41-7).
The preparation method comprises the following specific steps:
step one: firstly, weighing polyamide resin, adding the polyamide resin into a reaction bottle, adding a grafting agent into the reaction bottle, then enabling the polyamide resin in the reaction bottle to react with the grafting agent for a certain time, vacuumizing the reaction bottle after the reaction is completed, standing to obtain a sample A, adding a cross-linking agent into the sample A, performing normal pressure reaction for a certain time, and then performing reduced pressure reaction to obtain modified polyamide resin;
step two: weighing polyethylene glycol (CAS number: 25322-68-3), adding into a reactor, heating to a molten state, stirring and mixing uniformly, adding graphene oxide nanosheets (company: siami Biotechnology Co., ltd.), adding maleic anhydride into the reactor, refluxing, introducing dry air into the reactor, bubbling for a certain time, discharging unreacted maleic anhydride to obtain a sample B, weighing bamboo fibers, the sample B and the modified polyamide resin obtained in the step one, stirring and mixing to obtain a mixture;
step three: weighing the mixture obtained in the second step and the antibacterial agent for melting, filtering the melted material, and adding graphene, graphene hydrogel and an organic solvent into the filtered material for stirring and mixing to obtain a sample D;
step four: spinning the sample D obtained in the step three, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step five: and (3) processing the pre-oriented yarn obtained in the step (IV) through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the novel graphene polyamide filament.
Wherein: in the first step, the standing time is 2 hours, and the pressure after decompression is 0.07MPa.
The weight ratio of polyethylene glycol, graphene oxide nano-sheets and maleic anhydride in the second step is 0.4:0.5:1, stirring rate of 600r/min, bubbling time of 2h, and reflux time of 3h.
And fourthly, cooling the spinning in the step four by a water cooling mode.
Example 5
The novel graphene polyamide filament comprises the following raw materials in percentage by weight: 20% of polyamide resin, 16% of modified antibacterial agent, 7% of graphene, 4% of graphene hydrogel and 3% of organic solvent.
The antibacterial agent is nano silver antibacterial agent (company: hubei Chengfeng chemical Co., ltd.), and the organic solvent is n-butanol (CAS number: 71-36-3).
The preparation method comprises the following specific steps:
step one: weighing silver nitrate (CAS number: 7761-88-8), placing into a mixing bottle, adding water into the mixing bottle to obtain water solution, slowly adding cysteine (CAS number: 17817-88-8) water solution into the water solution, stirring with an electric stirring device to obtain sample C, adding tris (CAS number: 77-86-1) and NaBH into the sample C 4 Stirring and mixing the solution (company: shanghai Kaijin chemical engineering Co., ltd.), adding glacial acetic acid (CAS number: 76-49-3) for reaction, filtering the solution to obtain precipitate, and washing the precipitate with deionized water to obtain the modified antibacterial agent;
step two: weighing polyamide resin and the modified antibacterial agent obtained in the first step, melting, filtering the melted material, and adding graphene, graphene hydrogel and an organic solvent into the filtered material, and stirring and mixing to obtain a sample D;
step three: spinning the sample D obtained in the second step, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step four: and (3) processing the pre-oriented yarn obtained in the step (III) through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the novel graphene polyamide filament.
Wherein: silver nitrate, water, cysteine aqueous solution, tris (hydroxymethyl) aminomethane and NaBH in the step one 4 The weight ratio of the solution to glacial acetic acid to deionized water is 1:0.3:0.5:0.4:0.5:0.4:0.2, and the stirring speed is 900r/min. The stirring time is 1h, and the flushing time is 2h. The electric stirrer is an electromagnetic stirrer, and the spinning in the third step is cooled by water cooling.
Comparative example
The novel graphene polyamide filament comprises the following raw materials in percentage by weight: 20% of polyamide resin, 16% of antibacterial agent, 7% of graphene, 4% of graphene hydrogel and 3% of organic solvent.
The antibacterial agent is nano silver antibacterial agent (company: hubei Chengfeng chemical Co., ltd.), and the organic solvent is n-butanol (CAS number: 71-36-3).
The preparation method comprises the following specific steps:
step one: weighing polyamide resin and an antibacterial agent, melting, filtering the melted material, adding graphene, graphene hydrogel and an organic solvent into the filtered material, and stirring and mixing to obtain a sample D;
step two: spinning the sample D obtained in the step four, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step three: and D, treating the pre-oriented yarn obtained in the step five through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the novel graphene polyamide filament.
And cooling the spinning in the second step by a water cooling mode.
The novel graphene polyamide filaments prepared in the above examples 1 to 5 were taken as experiment group 1, experiment group 2, experiment group 3, experiment group 4 and experiment group 5, respectively, and the novel graphene polyamide filaments produced in the comparative example were selected as control groups, and the selected novel graphene polyamide filaments were tested for toughness, antibacterial rate, tensile strength and impact strength. (the antibacterial property of the selected novel graphene polyamide filaments is tested by referring to a method of GB20944.3-2008-T, the tensile strength of the selected novel graphene polyamide filaments is tested by referring to a method of GB/T14344-2008, the elongation at break is tested according to a standard of GB1040-92, the impact strength of the selected novel graphene polyamide filaments is tested by adopting a cantilever beam impact tester, and the insulation property is tested according to a standard of Q/GDSY 6050-20122.5.1). The test results are shown in Table 1.
Table 1 test results
| Elongation at break (%) | Antibacterial efficiency (%) | Tensile Strength (MPa) | Impact Strength (kJ/m 2) | arc/KV resistance | |
| Experiment group 1 | 130 | 94 | 64 | 8 | 153 |
| Experiment group 2 | 145 | 99 | 82 | 9 | 164 |
| Experiment group 3 | 136 | 97 | 73 | 6.5 | 158 |
| Experiment group 4 | 127 | 85 | 54 | 5.6 | 146 |
| Experiment group 5 | 121 | 76 | 47 | 4.3 | 135 |
| Control group | 113 | 73 | 43 | 2 | 129 |
As can be seen from Table 1, the antibacterial differentiated novel graphene polyamide filament produced by the method has better toughness, antibacterial property, tensile strength, impact strength and insulativity, the common antibacterial agent is added in comparative example 1 of example 4, the toughness, antibacterial property, tensile strength, impact strength and insulativity of example 1 are better, the common polyamide resin and the maleic anhydride, the grafting agent, the cross-linking agent and the bamboo fiber are not added in comparative example 1 of example 5, the toughness, antibacterial property, tensile strength, impact strength and insulativity of example 1 are better, the molecular branching degree of the polyamide resin is further improved through the primary modification of the grafting agent, the polychloroprene adhesive and the cross-linking agent, the intermolecular hydrogen bond is weakened, the flexibility of the polyamide resin is further improved, and the coupling effect of chemical bonds and hydrogen bonds can be achieved through the maleic anhydride added in the modified polyamide resin, so that the bonding strength of a two-phase interface is improved, the tensile strength of the modified polyamide resin and the metal-to-metal interface-modified polyamide resin is greatly improved, the antibacterial effect of the polar interface-modified polyamide resin is further improved, and the antibacterial effect of the metal-interface-modified polyamide-metal-polyamide-nano-polyamide-resin is greatly improved, and the antibacterial effect of the polar-modified metal-nano-polyamide-metal-alloy is further improved, and the polar-metal-interface-modified metal-modified-metal-nano-interface-metal-modified-polyamide-metal-alloy has better compatibility effect.
Claims (9)
1. Graphene polyamide filaments, characterized in that: comprises the following raw materials in percentage by weight: 20-30% of polyamide resin, 10-15% of maleic anhydride, 12-16% of grafting agent, 14-17% of cross-linking agent, 9-12% of bamboo fiber, 16-24% of modified antibacterial agent, 7-10% of graphene, 4-7% of graphene hydrogel and 3-6% of organic solvent;
the grafting agent is neoprene adhesive, and the cross-linking agent is protocatechuic aldehyde;
the preparation method comprises the following specific steps:
step one: firstly, weighing polyamide resin, adding the polyamide resin into a reaction bottle, adding a grafting agent into the reaction bottle, then enabling the polyamide resin in the reaction bottle to react with the grafting agent for a certain time, vacuumizing the reaction bottle after the reaction is completed, standing to obtain a sample A, adding a cross-linking agent into the sample A, performing normal pressure reaction for a certain time, and then performing reduced pressure reaction to obtain modified polyamide resin;
step two: weighing polyethylene glycol, adding the polyethylene glycol into a reactor, heating the polyethylene glycol to a molten state, stirring and mixing the polyethylene glycol and the graphene oxide nanosheets uniformly, adding maleic anhydride into the reactor, introducing dry air into the reactor after refluxing, bubbling for a certain time, discharging unreacted maleic anhydride to obtain a sample B, weighing bamboo fibers, the sample B and the modified polyamide resin obtained in the step one, stirring and mixing the mixture to obtain a mixture;
step three: weighing silver nitrate, putting into a mixing bottle, adding water into the mixing bottle to obtain an aqueous solution, slowly adding a cysteine aqueous solution into the aqueous solution, starting an electric stirring device for stirring to obtain a sample C, and adding tris (hydroxymethyl) aminomethane and NaBH into the sample C 4 The solution is prepared into a liquid preparation,stirring and mixing, adding glacial acetic acid for reaction, filtering the solution to obtain a precipitate, and finally flushing the precipitate with deionized water to obtain the modified antibacterial agent;
step four: weighing the mixture obtained in the second step and the modified antibacterial agent obtained in the third step, melting, filtering the melted material, and adding graphene, graphene hydrogel and an organic solvent into the filtered material, and stirring and mixing to obtain a sample D;
step five: spinning the sample D obtained in the step four, cooling and oiling the sample D after spinning is completed, and winding the sample D by a guide roller to obtain a pre-oriented yarn;
step six: and D, treating the pre-oriented yarn obtained in the step five through a guide roller, a hot box and a false twister, and winding the pre-oriented yarn again to obtain the graphene polyamide filament.
2. The graphene polyamide filament according to claim 1, wherein: comprises the following raw materials in percentage by weight: 22-28% of polyamide resin, 12-14% of maleic anhydride, 13-15% of grafting agent, 15-16% of cross-linking agent, 10-11% of bamboo fiber, 18-20% of modified antibacterial agent, 8-9% of graphene, 5-6% of graphene hydrogel and 4-5% of organic solvent.
3. The graphene polyamide filament according to claim 1, wherein: comprises the following raw materials in percentage by weight: 25% of polyamide resin, 12.5% of maleic anhydride, 14% of grafting agent, 15.5% of cross-linking agent, 10.5% of bamboo fiber, 20% of modified antibacterial agent, 8.5% of graphene, 5.5% of graphene hydrogel and 4.5% of organic solvent.
4. The graphene polyamide filament according to claim 1, wherein: the antibacterial agent is nano silver antibacterial agent, and the organic solvent is one of n-butanol or terpineol.
5. The graphene polyamide filament according to claim 1, wherein: the standing time in the first step is (2-3) h, and the pressure after decompression in the first step is (0.07-0.1) MPa.
6. The graphene polyamide filament according to claim 1, wherein: the weight ratio of polyethylene glycol, graphene oxide nano-sheets and maleic anhydride in the second step is (0.4-0.6): (0.5-0.7): 1, wherein the stirring rate in the second step is 500-600r/min, the bubbling time in the second step is (1-2) h, and the reflux time in the second step is (3-5) h.
7. The graphene polyamide filament according to claim 1, wherein: silver nitrate, water, cysteine aqueous solution, tris (hydroxymethyl) aminomethane and NaBH in the third step 4 The weight ratio of the solution to glacial acetic acid to deionized water is 1: (0.3-0.5): (0.5-0.8): (0.4-0.6): (0.5-0.7): (0.4-0.5): (0.2-0.4), wherein the electric stirring speed in the third step is 700-900r/min.
8. The graphene polyamide filament according to claim 1, wherein: the electric stirring time in the third step is (1-3) h, and the flushing time in the third step is (2-3) h.
9. The graphene polyamide filament according to claim 1, wherein: the electric stirrer in the third step is an electromagnetic stirrer, and the spinning in the fifth step is cooled by water cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210853556.XA CN115262029B (en) | 2022-07-20 | 2022-07-20 | Graphene polyamide filament and spinning method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210853556.XA CN115262029B (en) | 2022-07-20 | 2022-07-20 | Graphene polyamide filament and spinning method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115262029A CN115262029A (en) | 2022-11-01 |
| CN115262029B true CN115262029B (en) | 2024-01-26 |
Family
ID=83766915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210853556.XA Active CN115262029B (en) | 2022-07-20 | 2022-07-20 | Graphene polyamide filament and spinning method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115262029B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267348A (en) * | 2018-08-31 | 2019-01-25 | 陆海林 | A kind of preparation method and applications of the textile material added with graphene |
| CN111101290A (en) * | 2019-12-06 | 2020-05-05 | 湖北拓盈新材料有限公司 | Modified polyamide fiber non-woven fabric and preparation method thereof |
| CN112126251A (en) * | 2020-09-29 | 2020-12-25 | 镇江强龙新材料科技有限公司 | Preparation method and application of chelating functional nano-silver |
| CN113174129A (en) * | 2021-03-30 | 2021-07-27 | 江苏江山红化纤有限责任公司 | Antibacterial and antiviral graphene polyamide composite material and preparation method thereof |
| CN114716781A (en) * | 2022-04-29 | 2022-07-08 | 苏州博利迈新材料科技有限公司 | Preparation method of high-adhesion flame-retardant PA6 material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105862158A (en) * | 2016-06-08 | 2016-08-17 | 上海史墨希新材料科技有限公司 | Preparation method of graphene-chinlon nano-composite fibers |
-
2022
- 2022-07-20 CN CN202210853556.XA patent/CN115262029B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267348A (en) * | 2018-08-31 | 2019-01-25 | 陆海林 | A kind of preparation method and applications of the textile material added with graphene |
| CN111101290A (en) * | 2019-12-06 | 2020-05-05 | 湖北拓盈新材料有限公司 | Modified polyamide fiber non-woven fabric and preparation method thereof |
| CN112126251A (en) * | 2020-09-29 | 2020-12-25 | 镇江强龙新材料科技有限公司 | Preparation method and application of chelating functional nano-silver |
| CN113174129A (en) * | 2021-03-30 | 2021-07-27 | 江苏江山红化纤有限责任公司 | Antibacterial and antiviral graphene polyamide composite material and preparation method thereof |
| CN114716781A (en) * | 2022-04-29 | 2022-07-08 | 苏州博利迈新材料科技有限公司 | Preparation method of high-adhesion flame-retardant PA6 material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115262029A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6605756B2 (en) | Highly uniform colored polyester industrial yarn and method for producing the same | |
| Yu et al. | High-performance fully bio-based poly (lactic acid)/polyamide11 (PLA/PA11) blends by reactive blending with multi-functionalized epoxy | |
| CN1194121C (en) | Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation | |
| CN111718591B (en) | Lignin-containing bio-based composite material and preparation method thereof | |
| CN112538662B (en) | High-elasticity moisture-absorption antistatic PTT/PET composite fiber and preparation method thereof | |
| CN102250457A (en) | Long-fiberglass-reinforced polylactic acid composite material and preparation method thereof | |
| CN111875940A (en) | Toughened heat-resistant polylactic acid 3D printing wire and preparation method thereof | |
| CN111171520A (en) | Modified carbon nanotube reinforced shape memory epoxy resin composite material and preparation method thereof | |
| CN115262029B (en) | Graphene polyamide filament and spinning method thereof | |
| CN111499837A (en) | Self-repairing in-situ fluorescent tracing type heat-resistant weather-resistant epoxy resin and preparation method thereof | |
| CN102850738A (en) | PBT material used in optical fiber secondary coating, and preparation method and production system thereof | |
| CN103709742B (en) | A kind of modification of aramid fiber reinforced plastic PA66 material and preparation method thereof | |
| CN116041949B (en) | Preparation process of high-strength carbon nanotube modified nylon 6 composite material | |
| CN105622928B (en) | Branched polyamides and preparation method thereof | |
| CN111764156B (en) | Preparation method of high-performance polyimide fiber | |
| CN114182386A (en) | Functionalized graphene-polyester composite fiber and preparation method thereof | |
| CN113956653A (en) | Aramid fiber reinforced polyamide composite material and preparation method thereof | |
| CN114854180B (en) | Thermoplastic cellulose/PBAT composite film and preparation method thereof | |
| CN116693471B (en) | Bio-based epoxy chain extender, and preparation method and application thereof | |
| CN116790096A (en) | Preparation method of high-strength ultra-high molecular weight polyethylene fiber composite material | |
| Chao et al. | A review of modification processing and water⁃ soluble degradation ability of polyglycolic acid material | |
| CN117467246B (en) | Carbon fiber/glass fiber reinforced epoxy resin composite material and preparation method thereof | |
| CN114086269B (en) | Superfine denier porous polyester stretch textured yarn and processing technology thereof | |
| CN116535826B (en) | Solid-phase-tackified high-strength PBT and PET composite material and preparation method thereof | |
| TWI738137B (en) | Moisture absorption polyamide fiber having lower melting temperature and manufacture process thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |