CN108486678A - A kind of preparation method of graphene/polyamide 6 composite fibre - Google Patents
A kind of preparation method of graphene/polyamide 6 composite fibre Download PDFInfo
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- CN108486678A CN108486678A CN201810400953.5A CN201810400953A CN108486678A CN 108486678 A CN108486678 A CN 108486678A CN 201810400953 A CN201810400953 A CN 201810400953A CN 108486678 A CN108486678 A CN 108486678A
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- graphene
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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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a kind of preparation methods of graphene/polyamide 6 composite fibre, the composite material of graphene/polyamide 6 is obtained using in-situ polymerization, formic acid is added to dissolve obtained composite material, forms solution, the composite fibre of graphene/polyamide 6 is then prepared using wet spinning.The present invention is without high temperature, the condition of high pressure, economic and environment-friendly, the simple and quick obtained graphene/polyamide 6 complex fiber material of energy.
Description
Technical field
The present invention relates to technical field of fibre production, more particularly to the preparation side of a kind of graphene/polyamide 6 composite fibre
Method.
Background technology
Polyamide 6 itself has wear-resisting, oil resistant, self-lubricating, insulation, good mechanical performance, easy processing molding, weak acid and alkali resistance
Etc. excellent comprehensive performance, but common polyamide 6 is there is also the low defect of dry state and low temperature impact strength, make its application by
Certain limitation cannot meet the needs of industries such as vehicle electromechanical are to material high intensity.Pass through a variety of methods pair both at home and abroad
Common nylon carries out toughening modifying, the polyamide 6 after toughening be widely used in traffic, electronic apparatus, the consumer goods, mechanical industry and
Other industry.
The scientist Tomas Carothers outstanding from the nineteen thirty-five U.S. has synthesized PA66 in the lab, is the first conjunction in the world
At fiber, it is a very important milestone in polymer chemistry.Then there are the Buddhist nuns such as PA6, PA11, PA1010 again
Dragon.In last 100 years later, nylon is because of its distinctive excellent performance；And be widely used, PA6 is first by Germany within 1938
The P.Schlach of I.G.Farbon companies is researched and developed successfully, and nineteen forty-three, its production technology advanced optimized, and the performance of polyamide 6 obtains
Raising is arrived.
Currently, the preparation method of graphene/polyamide 6 composite fibre is mainly divided into two major class：Melt spinning route, should
Technique main flow is fiber-forming polymer under molten condition of 10-40 DEG C higher than its fusing point, forms relatively stable spinning melt,
Then by spinneret orifice extrusion molding, melt jet stream cooled and solidified in air or liquid medium forms Semifinished fibre, then passes through
The postprocessing working procedures such as overstretching, thermal finalization, become finished fiber.This production technology requires heat to the fusing point of polymer,
Thus the energy consumption in production process of melt spinning is high, and it is more complicated to be unfavorable for energy saving and entire production technology.Another kind of system
Standby route is electrostatic spinning route, which is：Nano-porous fiber is by the way that polymer is dissolved in high volatilization
Property solvent in, by the process of electrostatic spinning, high molecular fine liquid stream in high voltage electric field by high-speed stretch, solvent send out
Raw quickly volatilization, promotes liquid flow that quickly phase separation occurs, forms solvent-rich phase and polymer rich phase, polymer rich phase
Solidification ultimately forms fiber reinforcement, and solvent-rich phase then forms the duct of fiber.This production technology of electrostatic spinning：1. production
Efficiency is low, the production technology time comparable length of electrostatic spinning, so needing to take a substantial amount of time；2. governing factor is more traditional
Complicated many for spinning technique, voltage, flow, spinning distance, humidity, this few condition of temperature are all that can influence finally to spin
The quality of silk；3. equipment cost is high, the process equipment of general electrostatic spinning will include high voltage, and pump connects a device, controllably
Workbench；4. the consistency of product is relatively unstable.
Invention content
The purpose of the present invention is to provide a kind of preparation method of new graphene/polyamide 6 composite fibre, this method without
Need high temperature, high pressure condition, it is economic and environment-friendly, can simple and quick obtained graphene/polyamide 6 complex fiber material.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of preparation method of graphene/polyamide 6 composite fibre, includes the following steps：
(1) caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid solution are weighed, is added to reaction and holds
In device, condensed water is opened, starts to be passed through nitrogen, then under nitrogen protection atmosphere, heating while stirs, and is warming up to 200-
2-3 hour of 220 DEG C of insulation reactions then further heats up to 250-270 DEG C of insulation reaction 4-5h, after reaction, will be anti-
It answers product to be poured out from reaction vessel, obtains graphene/polymerization technology for polyamide 6 object；
(2) graphene/polymerization technology for polyamide 6 object is mixed with formic acid, is stirred 5-7 hours, standing and defoaming is spun for 2-3 hours
Silk solution；
(3) spinning solution is poured into glass syringe, spinning solution is pushed into syringe needle using pump is injected, is then led
Enter into water-filled hose；
(4) hose is taken out, is put into baking oven, dry 6-8 hour to get to graphene/polyamide 6 composite fibre.
Wherein hypophosphorous acid solution and manganese chloride are as light stabilizer.
The present invention using situ aggregation method produce graphene/polymerization technology for polyamide 6 object, the barrier property for the material produced,
Mechanical performance is stronger, and weight is lighter.
Preferably, caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid mass ratio be 9:1:
0.001-0.005:0.1-0.5:0.0025-0.0075。
Preferably, it is 0.3ml/s-0.5ml/s that spinning solution, which is pushed into the speed of injecting in syringe needle,.
Preferably, the interior diameter of syringe needle ranging from 1-5mm.
Preferably, a diameter of 1-6mm of hose.
Preferably, the coolant-temperature gage in water-filled hose is 20-40 DEG C.
Preferably, the temperature of baking oven is 80-100 DEG C.
Preferably, the content of graphene/polymerization technology for polyamide 6 object is 20%-30% (quality percentages in the spinning solution
Than).
The beneficial effects of the invention are as follows：Preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption greatly reduces, and obtains
The tensile strength of the composite fibre of graphene/polyamide 6 is higher.
Graphene of the present invention/polyamide 6 composite fibre, compares pure graphene fiber, and elongation at break is improved, compared
It is improved in the fracture strength of pure Fypro, composite fibre.
Description of the drawings
Fig. 1 is the infrared spectrogram of the composite fibre of graphene/polyamide 6 of the present invention.
Fig. 2 is the mechanical property figure of the composite fibre of graphene/polyamide 6 of the present invention.
Specific implementation mode
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
Embodiment 1：
A kind of preparation method of graphene/polyamide 6 composite fibre, includes the following steps：
(1) caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid solution are weighed, hypophosphorous acid solution is
The aqueous hypophosphorous acid of concentration 50%, water caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid quality
Than being 9:1:0.001:0.1:0.0025, it is added in reaction vessel, opens condensed water, start to be passed through nitrogen, then in nitrogen
It protects under atmosphere, heating while stirs, and is warming up to 3 hours of 200 DEG C of insulation reactions, then further heats up to 250 DEG C and protects
Temperature reaction 5h after reaction pours out reaction product from reaction vessel, obtains graphene/polymerization technology for polyamide 6 object, closes
Nitrogen and condensed water；
(2) by graphene/polymerization technology for polyamide 6 object, (a concentration of 85%) of formic acid mixes, and stirs 5 hours, stands with formic acid
Deaeration obtains spinning solution for 2 hours, and the mass percentage content of formic acid is 70% wherein in spinning solution, graphene/polyamide 6
The mass percentage content of polymer is 30%；
(3) spinning solution is poured into glass syringe, spinning solution is pushed into syringe needle using pump is injected, injects speed
Degree is 0.3ml/s, and the interior diameter ranging from 5mm of syringe needle is then introduced into water-filled hose, and coolant-temperature gage is 40 DEG C；
(4) hose is taken out, is put into 80 DEG C of baking ovens, dry 8 hours to get to the compound fibre of graphene/polyamide 6
Dimension.
Embodiment 2：
A kind of preparation method of graphene/polyamide 6 composite fibre, includes the following steps：
(1) caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid solution are weighed, hypophosphorous acid solution is
The aqueous hypophosphorous acid of concentration 50%, water caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid quality
Than being 9:1:0.005:0.5:0.0075, it is added in reaction vessel, opens condensed water, start to be passed through nitrogen, then in nitrogen
It protects under atmosphere, heating while stirs, and is warming up to 2 hours of 220 DEG C of insulation reactions, then further heats up to 270 DEG C and protects
Temperature reaction 4h after reaction pours out reaction product from reaction vessel, obtains graphene/polymerization technology for polyamide 6 object, closes
Nitrogen and condensed water；
(2) by graphene/polymerization technology for polyamide 6 object, (a concentration of 85%) of formic acid mixes, and stirs 7 hours, stands with formic acid
Deaeration obtains spinning solution for 3 hours, and the mass percentage content of formic acid is 80% wherein in spinning solution, graphene/polyamide 6
The mass percentage content of polymer is 20%；
(3) spinning solution is poured into glass syringe, spinning solution is pushed into syringe needle using pump is injected, injects speed
Degree is 0.5ml/s, and the interior diameter ranging from 1mm of syringe needle is then introduced into water-filled hose, and coolant-temperature gage is 20 DEG C；
(4) hose is taken out, is put into 100 DEG C of baking ovens, dry 6 hours to get to the compound fibre of graphene/polyamide 6
Dimension.
Embodiment 3：
A kind of preparation method of graphene/polyamide 6 composite fibre, includes the following steps：
(1) caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid solution are weighed, hypophosphorous acid solution is
The aqueous hypophosphorous acid of concentration 50%, water caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid quality
Than being 9:1:0.003:0.3:0.004, it is added in reaction vessel, opens condensed water, start to be passed through nitrogen, is then protected in nitrogen
It protects under atmosphere, heating while stirs, and is warming up to 2.5 hours of 210 DEG C of insulation reactions, then further heats up to 260 DEG C and protects
Temperature reaction 4.5h after reaction pours out reaction product from reaction vessel, obtains graphene/polymerization technology for polyamide 6 object, closes
Close nitrogen and condensed water；
(2) by graphene/polymerization technology for polyamide 6 object, (a concentration of 85%) of formic acid mixes, and stirs 6 hours, stands with formic acid
Deaeration obtains spinning solution for 2.5 hours, and the mass percentage content of formic acid is 75% wherein in spinning solution, graphene/polyamides
The mass percentage content of 6 polymer of amine is 25%；
(3) spinning solution is poured into glass syringe, spinning solution is pushed into syringe needle using pump is injected, injects speed
Degree is 0.4ml/s, and the interior diameter ranging from 1.45mm of syringe needle is then introduced into water-filled hose, and coolant-temperature gage is 30 DEG C；
(4) hose is taken out, is put into 90 DEG C of baking ovens, dry 7 hours to get to the compound fibre of graphene/polyamide 6
Dimension.
The product testing result of the present invention is as follows：
Fig. 1 is the infrared spectrogram of the composite fibre of graphene/polyamide 6 of the present invention, in 1640cm-1There is new peak
Value, corresponds to the stretching vibration of amide (C=O) key；In 1536cm-1There is new peak value, corresponds to the stretching of amide (N-H) key
Vibration.And the 2860 and 2930cm occurred-1Peak value show the stretching vibration of c h bond in PA6, these results all show stone
Black alkene is successfully grafted to PA6 chains.
Fig. 2 is the mechanical property figure of the composite fibre of graphene/polyamide 6 of the present invention.In fig. 2 it can be seen that graphite
The stress born when alkene/daiamid-6 fiber fracture is more much larger than pure daiamid-6 fiber, but graphene/daiamid-6 fiber
The deformation occurred when fracture is smaller than pure daiamid-6 fiber.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.
Claims (8)
1. a kind of preparation method of graphene/polyamide 6 composite fibre, which is characterized in that include the following steps：
(1) caprolactam, 6-aminocaprolc acid, manganese chloride, graphene oxide and hypophosphorous acid solution are weighed, reaction vessel is added to
In, condensed water is opened, starts to be passed through nitrogen, then under nitrogen protection atmosphere, heating while stirs, and is warming up to 200-220
It DEG C 2-3 hour of insulation reaction, then further heats up to 250-270 DEG C of insulation reaction 4-5h, it after reaction, will reaction production
Object is poured out from reaction vessel, obtains graphene/polymerization technology for polyamide 6 object；
(2) graphene/polymerization technology for polyamide 6 object is mixed with formic acid, is stirred 5-7 hours, it is molten that standing and defoaming obtains spinning in 2-3 hours
Liquid；
(3) spinning solution is poured into glass syringe, spinning solution is pushed into syringe needle using pump is injected, is then introduced into
In water-filled hose；
(4) hose is taken out, is put into baking oven, dry 6-8 hour to get to graphene/polyamide 6 composite fibre.
2. preparation method according to claim 1, which is characterized in that caprolactam, 6-aminocaprolc acid, manganese chloride, oxidation
The mass ratio of graphene and hypophosphorous acid is 9:1:0.001-0.005:0.1-0.5:0.0025-0.0075.
3. preparation method according to claim 1, which is characterized in that spinning solution is pushed into the speed of injecting in syringe needle and is
0.3ml/s-0.5ml/s。
4. preparation method according to claim 1, which is characterized in that the interior diameter of syringe needle ranging from 1-5mm.
5. preparation method according to claim 1, which is characterized in that a diameter of 1-6mm of hose.
6. preparation method according to claim 1, which is characterized in that the coolant-temperature gage in water-filled hose is 20-40 DEG C.
7. preparation method according to claim 1, which is characterized in that the temperature of baking oven is 80-100 DEG C.
8. preparation method according to claim 1, which is characterized in that graphene/polymerization technology for polyamide 6 in the spinning solution
The content of object is 20%-30%.
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| CN1234839A (en) * | 1996-10-25 | 1999-11-10 | 纳幕尔杜邦公司 | Process for making high tenacity aramid fibers |
| CN1882652A (en) * | 2003-10-20 | 2006-12-20 | 罗迪亚尼尔公司 | Light- and/or heat-stabilized composition |
| CN102926022A (en) * | 2011-08-09 | 2013-02-13 | 曹煜彤 | Preparation method for aromatic copolyamide fibers |
| CN106480532A (en) * | 2016-11-10 | 2017-03-08 | 过冬 | A kind of preparation method of Graphene reinforcing fiber |
| CN106621848A (en) * | 2016-12-21 | 2017-05-10 | 天津膜天膜科技股份有限公司 | Aliphatic polyamide hollow fiber membrane and preparation method and application thereof |
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