CN109680354A - A kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber - Google Patents
A kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber Download PDFInfo
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- CN109680354A CN109680354A CN201811580418.9A CN201811580418A CN109680354A CN 109680354 A CN109680354 A CN 109680354A CN 201811580418 A CN201811580418 A CN 201811580418A CN 109680354 A CN109680354 A CN 109680354A
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- Prior art keywords
- graphene
- polyethylene glycol
- preparation
- atnistatic
- neylon
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Classifications
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- 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
- D01F6/90—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 polyamides
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Abstract
The invention discloses a kind of graphene/polyethylene glycol Atnistatic neylon fiber preparation methods, it include: that esterification occurs by the hydroxyl of carboxyl and polyethylene glycol on graphene oxide to obtain poly ethyldiol modified graphene, modified graphene and 6 solution blending of nylon are reacted, obtain graphene polyvinyl alcohol nylon fiber using apparatus for melt spinning spinning.The present invention is by the graphene with superior electrical conductivity and has two kinds of antistatic agents of hydrophilic polyethylene glycol compound, not only reduce the reunion of graphene, and improve and greatly improve antistatic property, obtained modification of nylon fiber can be applied to the fields such as function textile fabric, conductive material, anti-static material.
Description
Technical field
The present invention relates to functional fibre fields, and in particular to a kind of system of graphene/polyethylene glycol Atnistatic neylon fiber
Preparation Method.
Background technique
With advances in technology and expanding economy, increasing living standard promotion functions fiber is to high-performance
The directions such as change, multifunction and intelligence are developed.Polycaprolactam, also known as nylon 6 (PA6) have excellent wearability, corrosion resistant
Erosion, oil resistant, solvent resistant and processing performance etc., but since PA6 sheet resistance is up to 1013Ω, in processing, production and use process
In, mantle friction generate charge simultaneously gather, to a certain extent when will cause it is various potentially hazardous, in order in practical applications
The harm for avoiding electrostatic accumulation from generating needs to carry out antistatic treatment to nylon 6.
Therefore, it is to improve a kind of simple and effective side of nylon fiber electric conductivity that conductive filler is added in fibre-forming polymer
Method.Graphene is by the tightly packed carbon material at single layer hexagonal lattice of sp2 hydbridized carbon atoms, is most thin in the world
Two-dimensional material, sp2 key have high-intensitive and stability, so that graphene has high-intensitive and thermal conductivity；Another is flat with carbon atom
The vertical σ in facezOrbital electron then forms big pi bond in lattice plane two sides, assigns the excellent electric conductivity of graphene, high electron mobility
The characteristics such as rate.Graphene mechanics outstanding, optical property and electronic conduction ability make it in catalysis, biology, electronics, photo-thermal
The high potentiality to be exploited and application value that the fields such as, energy storage, photoelectric device and composite material have.
Polyethylene glycol and nylon 6 have preferable compatibility, effect stability, lasting, the work of reinforced nylon 6 antistatic property
As follows with mechanism: (1) ehter bond contained in polyethylene glycol belongs to hydrophilic radical, further enhances its suction after being added to nylon 6
It is moist, water membrane is formed on 6 surface of nylon, accelerates the loss of charge, (2) peg molecule chain flexibility is good, is added to
Play the role of plasticising in nylon 6, reduce activation energy, accelerates conduction of the charge between segment.(3) some polyethylene glycol
Reaction is not participated in, but is coexisted in the form of blending with PA6 matrix, is dispersed in the base, in nylon 6, the phase of polyethylene glycol
One layer thin of moisture conductive layer is formed on interface, while PEG dispersed particle contacts with each other in matrix, be formed from inside to
The passage of water on surface is conducive to electrostatic charge leakage.
Since graphene is nano-grade size, there are serious agglomerations, it is difficult to nylon 6 mixing, secondly, graphene
Density ratio nylon resin it is much smaller, when processing, is difficult to dissolve each other with nylon 6, it is difficult to promoted and applied in terms of Polymer Processing, because
This urgent need solves the problems, such as graphene dispersion mixing in nylon resin.Moreover, antistatic agent used at present acts on single, mesh
The preceding research used about composite antistatic agent in nylon 6 it is less.
Summary of the invention
In order to overcome shortcoming and deficiency of the existing technology, it is antistatic that the present invention provides a kind of graphene/polyethylene glycol
The preparation method of nylon fiber.
The present invention adopts the following technical scheme:
A kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber, includes the following steps:
Under nitrogen protection, graphene oxide is put into dimethyl sulfoxide by S1, stirs simultaneously ultrasonic disperse 10-50min,
Then condensing agent N, N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is added, stirs simultaneously ultrasonic disperse 0.5~2 hour,
It adds 4- lutidines and dissolves the dimethyl sulphoxide solution of polyethylene glycol, continue stirring ultrasonic reaction 12~24 hours,
Precipitation in acetone obtains poly ethyldiol modified graphene crude product；
The poly ethyldiol modified graphene crude product of S2 is add to deionized water and is heated to 30-80 DEG C, molten in acetone
Solution is precipitated, filters and washs, is dried to obtain the polyvinyl alcohol modification graphene of purifying；
The poly ethyldiol modified graphene dispersion of purifying in formic acid, is ultrasonically treated 10-50min by S3；
Caprolactam, adipic acid and catalyst is added in S4 in a high pressure reaction kettle, is heated to 205-210 in a nitrogen atmosphere
DEG C, pressure is maintained at 0.2~0.4MPa, after being kept for 2~3 hours, is warming up to 260~270 DEG C, poly ethyldiol modified graphite is added
Alkene vacuumizes, and reacts 1~2 hour, is passed through nitrogen after reaction and extrudes material, cooling and dicing obtains graphene/poly- second two
Alcohol nylon 6 composite material master batch；
S5 by graphene/polyethylene glycol nylon 6 composite material master batch it is dry after, carry out melt spinning, obtain graphene/
Polyethylene glycol nylon fiber.
Graphene oxide in the S1 is to pass through modified Hummers method preparation by graphite.
The molar ratio of the N, N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is (1.0-1.2): 1.
The catalyst is 4- lutidines, and dosage is 5~10%.
Poly ethyldiol modified graphene in the S4, in graphene/polyethylene glycol nylon 6 composite material master batch of preparation
Mass fraction be 0.1~0.3%.
In the S5, melt spinning, actual conditions are carried out with melt spinning machine are as follows: spinning voltage is 18~20kV, is connect
Receiving distance is 10-15cm, fltting speed 0.05-0.2mL/h.
Beneficial effects of the present invention:
(1) present invention is changed using the reactive functional groups on polyethylene glycol with graphene surface functional group reactions
Property graphene, improve compatibility and dispersibility of the graphene in nylon 6 resin；
(2) two kinds of antistatic agents of the invention are compound, obtain graphene/polyethylene glycol nylon fiber, with excellent permanent
The composite anti-static system of antistatic property.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber, includes the following steps:
Under nitrogen protection, 0.1g graphene oxide will be put into 10mL dimethyl sulfoxide, and will stir simultaneously ultrasonic disperse
30min。
Condensing agent N, N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is added, stirs and ultrasonic disperse 1~2 is small
When, it adds 4- lutidines and dissolves the dimethyl sulphoxide solution of 2g polyethylene glycol, continue to stir ultrasonic reaction 12~24
Hour, Precipitation obtains polyvinyl alcohol modification graphene in acetone.
The precipitating that above-mentioned steps are obtained is add to deionized water and is heated to 80 DEG C, re-dissolves, then in acetone
Middle precipitation filters, washing, repeats this step three times, be dried to obtain the polyvinyl alcohol modification graphene of purifying.
It disperses modified graphene in formic acid, is ultrasonically treated 30min.
A certain amount of caprolactam, adipic acid and catalyst are added in a high pressure reaction kettle, is heated in a nitrogen atmosphere
205~210 DEG C, pressure is maintained at 0.2~0.4MPa, after being kept for 2~3 hours, is warming up to 260~270 DEG C, mass fraction is added
It for 0.2% poly ethyldiol modified graphene, vacuumizes, reacts 1~2 hour, be passed through nitrogen after reaction and extrude material, it is cooling
Pelletizing obtains graphene/polyethylene glycol nylon 6 composite material master batch.
After above-mentioned 6 master batch of resulting nylon is dry, melt spinning is carried out with melt spinning machine, obtains graphene/poly- second
Glycol nylon fiber, the breaking strength 3.0cN/dtex of fiber, elongation at break 55%, surface resistivity (Ω) be 4.6 ×
107。
Embodiment 2
A kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber, includes the following steps:
Under nitrogen protection, 0.2g graphene oxide will be put into 20mL dimethyl sulfoxide, and will stir simultaneously ultrasonic disperse
40min。
Condensing agent N, N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is added, stirs and ultrasonic disperse 1~2 is small
When, it adds 4- lutidines and dissolves the dimethyl sulphoxide solution of 2g polyethylene glycol, continue stirring ultrasonic reaction 20 hours,
Precipitation obtains polyvinyl alcohol modification graphene in acetone.
The precipitating that above-mentioned steps are obtained is add to deionized water and is heated to 80 DEG C, re-dissolves, then in acetone
Middle precipitation filters, washing, repeats this step three times, be dried to obtain the polyvinyl alcohol modification graphene of purifying.
It disperses modified graphene in formic acid, is ultrasonically treated 50min.
A certain amount of caprolactam, adipic acid and catalyst are added in a high pressure reaction kettle, is heated in a nitrogen atmosphere
205~210 DEG C, pressure is maintained at 0.2~0.4MPa, after being kept for 2~3 hours, is warming up to 260~270 DEG C, mass fraction is added
It for 0.2% poly ethyldiol modified graphene, vacuumizes, reacts 1.5 hours, be passed through nitrogen after reaction and extrude material, it is cooling
Pelletizing obtains graphene/polyethylene glycol nylon 6 composite material master batch.
After above-mentioned 6 master batch of resulting nylon is dry, melt spinning is carried out with melt spinning machine, obtains graphene/poly- second
Glycol nylon fiber, the breaking strength 2.8cN/dtex of fiber, elongation at break 50%, surface resistivity (Ω) be 6.5 ×
107。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of graphene/polyethylene glycol Atnistatic neylon fiber preparation method, which comprises the steps of:
Under nitrogen protection, graphene oxide is put into dimethyl sulfoxide by S1, stirs simultaneously ultrasonic disperse 10-50min, then
Condensing agent N, N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is added, stirs simultaneously ultrasonic disperse 0.5~2 hour, then plus
Enter 4- lutidines and dissolve the dimethyl sulphoxide solution of polyethylene glycol, continues stirring ultrasonic reaction 12~24 hours, third
Precipitation in ketone obtains poly ethyldiol modified graphene crude product；
The poly ethyldiol modified graphene crude product of S2 is add to deionized water and is heated to 30-80 DEG C, dissolves in acetone, analyses
Out, it filters and washs, be dried to obtain the poly ethyldiol modified graphene of purifying；
The poly ethyldiol modified graphene dispersion of purifying in formic acid, is ultrasonically treated 10-50min by S3；
Caprolactam, adipic acid and catalyst is added in S4 in a high pressure reaction kettle, is heated to 205-210 DEG C in a nitrogen atmosphere,
Pressure is maintained at 0.2~0.4MPa, after being kept for 2~3 hours, is warming up to 260~270 DEG C, poly ethyldiol modified graphene is added,
It vacuumizes, reacts 1~2 hour, be passed through nitrogen after reaction and extrude material, cooling and dicing obtains graphene/polyethylene glycol Buddhist nun
Imperial 6 composite material master batches；
S5 carries out after graphene/polyethylene glycol nylon 6 composite material master batch drying melt spinning, obtains graphene/poly- second
Glycol nylon fiber.
2. a kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber according to claim 1, feature exist
In the graphene oxide in the S1 is to pass through modified Hummers method preparation by graphite.
3. a kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber according to claim 1, feature exist
In, the N, the molar ratio of N '-dicyclohexylcarbodiimide and I-hydroxybenzotriazole is (1.0-1.2): 1.
4. a kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber according to claim 1, feature exist
In the catalyst is 4- lutidines.
5. a kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber according to claim 1, feature exist
In, in the S4, the matter of the poly ethyldiol modified graphene in graphene/polyethylene glycol nylon 6 composite material master batch of preparation
Measuring score is 0.1~0.3%.
6. a kind of preparation method of graphene/polyethylene glycol Atnistatic neylon fiber according to claim 1, feature exist
In carrying out melt spinning, actual conditions with melt spinning machine in the S5 are as follows: spinning voltage is 18~20kV, receives distance
For 10-15cm, fltting speed 0.05-0.2mL/h.
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Cited By (6)
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| CN110483979A (en) * | 2019-08-26 | 2019-11-22 | 福建华彩新材料有限公司 | A kind of graphene oxide masterbatch and its preparation and application |
| CN110559877A (en) * | 2019-09-26 | 2019-12-13 | 哈尔滨工程大学 | Preparation method and application of hydrophilic and antibacterial dual-modified ultrafiltration membrane |
| US10766167B1 (en) | 2020-01-10 | 2020-09-08 | Prince Mohammad Bin Fahd University | Method of forming thermally and electrically conductive polyolefin-carbon nanomaterial composite having breakdown-induced electrical conduction pathways |
| CN112226058A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Antistatic heat conduction material and preparation method and application thereof |
| CN112920415A (en) * | 2021-01-11 | 2021-06-08 | 华南理工大学 | Amidated graphene/nylon 6 nanocomposite and preparation method thereof |
| CN113279260A (en) * | 2020-12-31 | 2021-08-20 | 深圳联达技术实业有限公司 | Multifunctional graphene composite fiber for back cushion and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112226058A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Antistatic heat conduction material and preparation method and application thereof |
| CN112226058B (en) * | 2019-07-15 | 2023-07-04 | 中国石油化工股份有限公司 | Antistatic heat conduction material and preparation method and application thereof |
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| US10766167B1 (en) | 2020-01-10 | 2020-09-08 | Prince Mohammad Bin Fahd University | Method of forming thermally and electrically conductive polyolefin-carbon nanomaterial composite having breakdown-induced electrical conduction pathways |
| US11072095B1 (en) | 2020-01-10 | 2021-07-27 | Prince Mohammad Bin Fahd University | Method of applying voltage to a polymer/graphene composite to form a conductive polyolefin-carbon nanomaterial |
| US11213974B2 (en) | 2020-01-10 | 2022-01-04 | Prince Mohammad Bin Fahd University | Method for making polyethylene/graphene composite |
| CN113279260A (en) * | 2020-12-31 | 2021-08-20 | 深圳联达技术实业有限公司 | Multifunctional graphene composite fiber for back cushion and preparation method thereof |
| CN112920415A (en) * | 2021-01-11 | 2021-06-08 | 华南理工大学 | Amidated graphene/nylon 6 nanocomposite and preparation method thereof |
| CN112920415B (en) * | 2021-01-11 | 2022-05-24 | 华南理工大学 | Amidated graphene/nylon 6 nanocomposite and preparation method thereof |
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Application publication date: 20190426 |