CN106948171A - A kind of post-processing approach of fibre, obtained modified fibre product and application thereof - Google Patents
A kind of post-processing approach of fibre, obtained modified fibre product and application thereof Download PDFInfo
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- CN106948171A CN106948171A CN201710197196.1A CN201710197196A CN106948171A CN 106948171 A CN106948171 A CN 106948171A CN 201710197196 A CN201710197196 A CN 201710197196A CN 106948171 A CN106948171 A CN 106948171A
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- graphite alkenes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B17/00—Selection of special materials for underwear
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
Abstract
The present invention relates to a kind of post-processing approach of fibre, methods described includes：By fibre impregnated graphite alkenes material dispersion liquid, the elastomeric state temperature of fibrous material is warming up to after taking-up, and constant temperature carries out Combined Processing, afterwards through supercooling, drying, obtains composite fiber product.The present invention is realized in the inside and outside while the uniformity and fastness that graphite alkenes material is present in the purpose of composite graphite alkenes material, increase fiber of fiber；Improve the electric conductivity of fibre；Enhance the far infrared performance of fibre；The preparation method that the present invention is provided effectively can dose graphite alkenes material to fibrous inside, simultaneously in fibrous external coated graphite alkenes material, by fibre impregnated graphite alkenes substance solution, heat treatment is carried out afterwards and realizes graphene being uniformly distributed on fiber.
Description
Technical field
The invention belongs to fiber preparation field, and in particular to a kind of post-processing approach of fibre, obtained modified fibre
Fiber products and application thereof.
Background technology
The development of conductive fiber starts from 1960s, conductive fiber typically refer under standard environment (20 DEG C of temperature,
Humidity 65%), ratio resistance is less than 107Ω·cm.Its development course generally comprises 4 stages：Metallic fiber, carbon fiber and carbon containing
The composite conducting fiber of black composition polymer, the conductive fiber containing metal salt, conduction high polymer conductive fiber.Although conductive
Fiber has obtained significant progress, but there is also it is certain the problem of, such as by metallic conduction fiber and plate metal conductive fiber system
Into fabric feeling it is coarse, comfortableness is poor, and conducting polymer technique is more complicated, seriously polluted.Furthermore, pass through coating or letter
The attachment of fiber or the graphene of fibre prepared by single impregnation technology is insecure, and additional work(is just lost after washing repeatedly
Energy.Therefore, develop that the new new method for preparing conductive fiber is significant and actual application prospect.
Graphene is a kind of two-dimensional material for the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, with many excellent
Different performance (high-strength, high heat conduction, highly conductive, high lightweight), while also possessing big pi-conjugated system.It has been found since 2004,
Graphene just becomes a big study hotspot of scientific circles.While the physicochemical properties to graphene are studied, with
The related composite of graphene emerges in an endless stream.Graphene is combined by prior art with textile fabric, it is desired to be able to had
While the functional fiber fiber such as electric conductivity and far infrared, firmness of the graphene on fiber is further ensured, makes it
Function does not decay significantly because of increasing for washing times.
This area needs to develop a kind of post-processing approach to fibre, and it can realize jail of the graphene on fiber
Gu it is compound, improve the electric conductivity of fiber.
The content of the invention
It is an object of the invention to provide a kind of post-processing approach of fibre, methods described includes：By fibre
Impregnated graphite alkenes material dispersion liquid, is warming up to the elastomeric state temperature of fibrous material after taking-up, and constant temperature carries out Combined Processing, it
By supercooling, drying, composite fiber product is obtained.
Fibre is immersed in graphite alkenes material dispersion liquid by the present invention, such as is at normal temperatures impregnated fibre
, can be by the absorption of graphite alkenes material in the outside of the fibre in graphite alkenes material dispersion liquid, taking-up is adsorbed
The fibre of graphite alkenes material, and the elastomeric state temperature of fibrous material is warming up to, the space of fibrous inside is increased, had time
Gap becomes big, and the graphite alkenes material adsorbed in fibrous external can be moved in the space, cooled down afterwards, fibrous inside
Space reduces, and realizes that graphite alkenes material is solidificated in the purpose of fibrous inside.
Those skilled in the art are it will be clearly understood that fibrous inside of the present invention and fibrous external are well known in the art general
Read, it is understood that the macromolecular into fiber is in space clustering formation supramolecular structure, the inside of the macromolecular aggregation in groups
There is the region between crystal region, noncrystalline domain and crystal region and noncrystalline domain；And macromolecular aggregation finishes the outside to be formed and seen
Do the outside of fiber.
Preferably, the post-processing temperature is higher than the glass transition temperature of fibrous material in fibre more than 5 DEG C.Than
High more than 5 DEG C of the glass transition temperature of fibrous material is conducive to the wriggling of fiber molecule, and it is rapider that space is opened, graphene
The time that class material enters space is shorter.
Preferably, the concentration of the graphite alkenes material dispersion liquid be 0.1~5wt%, preferably 0.3~2wt%, for example
0.3%th, 0.5%, 0.8%, 0.9%, 1.3%, 1.6%, 1.8%, 1.9%, 1.5%, 3%, 3.6%, 4%, 4.5% etc.,
It is preferred that 0.3~2wt%.
Preferably, the particle diameter of the graphite alkenes material in the graphite alkenes material dispersion liquid is no more than 20 μm；It is preferred that
For 100nm~10 μm, further preferred 200nm~5 μm；Such as 30nm, 150nm, 190nm, 230nm, 260nm, 290nm,
330nm, 460nm, 590nm, 630nm, 760nm, 890nm, 930nm, 1 μm, 3 μm, 8 μm, 11 μm, 13 μm, 18 μm etc..
For dip time of the fibre in the graphite alkenes material dispersion liquid, the present invention is not specifically limited,
That exemplary can be 5~30min, such as 6min, 9min, 13min, 16min, 22min, 25min, 26min, 28min.
The elastomeric state temperature of fibrous material is warming up to, the process that constant temperature carries out Combined Processing is carried out under solvent-free effect,
It can for example be heated using environment temperature, such as hot air lamp, exemplary such as greenhouse, baking oven heating.
Preferably, the mode of the heating is hot air.
Carried out for the high-elastic thermostatic that fibrous material is warming up to after the fibre taking-up of impregnated graphite alkenes material
The time of Combined Processing is not specifically limited, and that exemplary can be 15~120min；Such as 16min, 19min, 23min,
26min, 32min, 55min, 66min, 73min, 78min, 85min, 88min, 95min etc..
Preferably, nano-cellulose is added with the graphite alkenes material dispersion liquid.
The addition of appropriate nano-cellulose, which can be improved, is wrapped in graphite alkenes material on the fiber, and Nanowire
The winding of dimension element can improve the intensity of the composite fibre.
Preferably, the diameter of the nano-cellulose is not more than 10nm, and draw ratio is not less than 10；
Preferably, concentration of the nano-cellulose in dispersion liquid be below 2wt%, preferably below 1wt%, further preferably
Below 0.5wt%.
Nano-cellulose is in itself wire, and it fibrous external can circumferentially be wound again, and this canoe can be improved
The intensity of fiber, and firmness of the graphene in fibrous external can be improved；On the other hand, one end of nano-cellulose can
Insert in graphene sheet layer, improve adhesion amount of the graphite alkenes material on fiber.But nano-cellulose is non-conductive in itself, mistake
Many nano-celluloses can cause the decline of electric conductivity.
Preferably, the graphite alkenes material includes graphene, biomass graphene, graphene oxide, graphene derivative
Any a kind or at least two kinds of of mixing of thing, preferably graphene and/or biomass graphene.
Signified grapheme material of the invention includes graphene, biomass graphene, graphene oxide, graphene and derived
Thing, they can be by different process preparation, or different raw material are prepared, for example, mechanical stripping method, oxidation are also
Former method, the biomass graphene prepared by resource of biomass by charing and atomic rearrangement etc..Graphene of the present invention
Material (or graphite alkenes material) refers to the different types of graphene that those skilled in the art can prepare in principle.
Preferably, the Graphene derivative includes any 1 in element doping graphene or functional group's graphite alkene thing
Plant or at least two kinds of combinations.
Graphene oxide electric conductivity itself is poor, in order to ensure the electric conductivity for the fiber being combined by graphene oxide, this
Invention can carry out reduction treatment to the modified fibre product for being compounded with graphene oxide.
When the graphite alkenes material is graphene oxide, reduction treatment is carried out before cooling and/or afterwards.
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process.
Preferably, the reducing agent reducing process is reduced including adding reducing agent.
Preferably, the addition of the reducing agent is the 10~200wt%, preferably 50~100wt% of graphite alkenes material.
Preferably, the reducing agent includes ascorbic acid, hydrazine hydrate, glucose, ethylenediamine, sodium citrate, the Guang ammonia of L- half
Any a kind or at least two kinds of of combination in acid, hydroiodic acid or sodium borohydride.
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced.
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reduction are passed through
Property atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
In technical solutions according to the invention, the modified fibre product is not particularly limited.Preferably, the fibre
Fiber products include any a kind or at least two kinds of of combination in fiber precursor, yarn and fabric；
Preferably, the fiber of the fibre can be any fiber that those skilled in the art can be known, example
Property the fiber include polyester fiber, nylon fibre, spandex fibre, aramid fiber, acrylic fiber, PVA fibers, regenerated fiber
Cellulose fiber.
Those skilled in the art will be apparent to the skilled artisan that for yarn and fabric there is a situation where blending, such as terylene and regenerated cellulose
The blending of fiber, blending of polyamide fibre, acrylic fibers and nylon etc.；Because the elastomeric state temperature range of various fibrous materials is different, so
Institute in " by fibre impregnated graphite alkenes material dispersion liquid, the elastomeric state temperature of fibrous material is warming up to after taking-up " of the invention
The elastomeric state temperature for being warming up to fibrous material referred to generally refers to a kind of larger fibrous material of accounting in scribbled or fabric
Elastomeric state temperature.
The yarn can be the yarn that any mode that those skilled in the art can be known is made, such as by any energy
The unmodified fibers list enough obtained is spun, blending, or is carried out by the modified fibre post-processed by foregoing mode
Single spinning, blending, or obtained by the unmodified fibers with modified fibre blending.It should be clear that in order to ensure fiber system
The electric conductivity of product, generally fibrous material all in fibre should all contain grapheme material.
The fabric can be the fabric that any mode that those skilled in the art can be known is made, for example, changed by described
Any a kind in property fiber, modified yarn, unmodified fibers, unmodified yarn or at least two kinds of weaved.Should be bright
Really, in order to ensure the electric conductivity of fibre, generally the overwhelming majority should be by graphene in fibre
The fibrous material of material modification.
Preferably, the post-processing approach of the fibre comprises the following steps：
(A1) fibre is impregnated into the first graphite alkenes material dispersion liquid, elastomeric state temperature is warming up to after taking-up,
Constant temperature carries out first time Combined Processing under post-processing temperature；Graphite alkenes material in the first graphite alkenes material dispersion liquid
Particle diameter be less than 1 μm；
(A2) fibre after first time Combined Processing is impregnated into the second graphite alkenes material dispersion liquid, after taking-up
It is warming up to after the second post-processing temperature, constant temperature carries out second of Combined Processing, afterwards through supercooling, drying, obtains composite fibre
Product；The particle diameter of graphite alkenes material is 1~20 μm in the second graphite alkenes material dispersion liquid.
Because the size in fibrous inside space is limited, step (A1) only with 1 μm of particle diameter ＜ graphite alkenes material to fibre
Fiber products are modified, it is well known that graphene particle diameter is smaller to be less susceptible to disperse, easier to reunite, therefore are often selected low
The graphene solution of concentration, so also saves the consumption of graphene, and reduces big particle diameter graphite alkenes material blocking space
Probability, improve the adhesion amount of graphene.It is 1~20 μm of graphite alkenes material to fibre that step (A2), which uses particle diameter,
It is modified compound, big particle diameter graphite alkenes material can be made to be present in fibrous external in the way of coating, fit, be more beneficial for
Graphene is in fibrous external formation conductive network, additionally it is possible to play a part of closing fibrous inside space, by increasing capacitance it is possible to increase graphene
The fastness of class material in the fibre.
The two of the object of the invention are to provide the modified fibre product that a kind of post-processing approach as described in the first purpose is obtained, institute
State modified fibre product fibrous inside exist outside graphite alkenes material, the fiberoptic fiber of the modified fibre product there is also
Graphite alkenes material.
Modified fibre product prepared by the method for the invention, can realize that fibrous inside and outside Monodispersed have graphene
Purpose, improve graphite alkenes material being uniformly distributed in fiber radial direction, add the compound quantity of graphene, improve fiber
Electric conductivity, improve graphite alkenes material on fiber be combined fastness.
The graphite alkenes material ratio outside the modified fibre product is preferably, there are to be present in modified fibre product
The graphite alkenes material in portion is more.There is more graphite alkenes material, in modified fibre product outside the modified fibre product
Outside such as modified fibre can overlap, and preferably improve the electric conductivity of the modified fibre product.
Fiber has macromolecular material aggregation to obtain, and macromolecular is regular mutually neatly stable to be arranged in height
The geometrical regularity of degree, as crystalline texture or crystalline state.The region of the regular proper alignment of fiber macromolecular turns into crystallization
Area；In crystal region macromolecular chain segment arranged regular, close structure, gap and hole are less, and inter-molecular binding force is strong.Fiber divides greatly
The disorderly region arranged is noncrystalline domain to son at random, in noncrystalline domain, macromolecular chain segment fall into disarray, random, structure
Loosely, there are more gap and hole, the power that be combined with each other is small.
Preferably, the gross mass of graphite alkenes material is modified fibre product gross mass in the modified fibre product
0.5~3%.Graphite alkenes content of material should not be excessive, is excessively easily caused fibre strength reduction, the wasting of resources.
Preferably, the fibrous inside of the modified fibre product includes crystal region, noncrystalline domain and crystal region and non-knot
Gap between crystalline region；
Preferably, there is graphite alkenes material in the fibrous inside crystal region of the modified fibre product, while the modification
There is graphite alkenes material in the fibrous external of fibre.
Gap of the present invention, space, hole can be replaced mutually, represent the space of fibrous inside.
Preferably, in the composite fibre, graphite alkenes material accounts for 0.5~3wt% of composite fibre, such as 0.6wt%,
0.7wt%, 0.9wt%, 1.1wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.7wt%, 1.9wt%, 2.1wt%,
2.2wt%, 2.4wt%, 2.6wt%, 2.7wt%, 2.9wt% etc..
Preferably, particle diameter≤20 μm of the graphite alkenes material, such as 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5
μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm etc..
Preferably, 1 μm of the particle diameter ＜ for the graphite alkenes material that the modified fibre product fibrous inside is present, such as 0.05
μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm etc..
Preferably, the particle diameter for the graphite alkenes material that the modified fibre product fibrous external is present is 1~20 μm, for example
1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm etc..
Preferably, when the graphite alkenes material is graphene and/or biomass graphene, the modified fiber materials
Ratio resistance≤1 × 105Ω；
Preferably, when the graphite alkenes material is graphene and/or biomass graphene, the modified fibre product
After washing 50 times, ratio resistance≤1 × 10 of its modified fiber materials5Ω。
Preferably, when the graphite alkenes material is graphene oxide and/or biomass graphene, the modified fibre
After product is washed 50 times, its far infrared normal emittance is not less than 0.85, for example, be not less than 0.87, is not less than 0.88, not low
In 0.90.
Preferably, the modified fibre product includes modified fibre, the yarn comprising modified fibre and includes modified fibre
Fabric in any a kind or at least two kinds of of combination；
Preferably, the modified fibre includes modified polyester fibre, modified nylon fiber, modified spandex fibre, modified virtue
Synthetic fibre fiber, modified acrylic fibres, modified PVA fiber, modification regeneration cellulose fibre；
Preferably, the yarn comprising modified fibre is spun by the modified fibre list, blending or mixed with unmodified fibers
Spinning is obtained；
Preferably, the fabric comprising modified fibre is by the modified fibre and the yarn system for including modified fibre
Into.
In order to further improve the intensity of the modified fibre product and the fastness of graphite alkenes material, described modification
Contain nano-cellulose in fibre.The addition of appropriate nano-cellulose can be improved is wrapped in institute by graphite alkenes material
State on fiber, and the winding of nano-cellulose can improve the intensity of the modified fibre product.
Preferably, it is compounded with nano-cellulose in the modified fibre of the modified fibre product.
Preferably, the nano-cellulose is wrapped in the modified fibre internally and/or externally.Refer specifically to, Nanowire
Dimension element is by high draw ratio and small diameter, by outside graphite alkenes material and fibrous inside crystal region or fibrous inside graphite
Alkenes material is bundled or overlapped so that outside graphite alkenes material is difficult for drop-off.
The three of the object of the invention are to provide a kind of purposes of the modified fibre product as described in the second purpose, the modified fibre
Product is used to prepare home textile, underwear, protective garment, thermal cloth, socks.
Compared with prior art, the present invention has the advantages that：
(1) fibre impregnated graphite alkenes material dispersion liquid is warming up to the elastomeric state of fibrous material by the present invention afterwards
Temperature, and constant temperature post-processed, and is made the graphite alkenes motion of matter of attachment to the fibrous inside of fibre, is realized in fiber
Inside and outside while the purpose of composite graphite alkenes material, graphite alkenes material is present in increase fiber uniformity and jail
Solidity；
(2) present invention can improve the electric conductivity of fibre by adding graphene and/or biomass graphene；
Addition graphene oxide and/or biomass graphene further enhancing the far infrared performance of fibre；
(3) preparation method that the present invention is provided effectively can dose graphite alkenes material to fibrous inside, while
Fibrous external coated graphite alkenes material, by fibre impregnated graphite alkenes substance solution, carries out heat treatment realization afterwards
Graphene being uniformly distributed on fiber.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Embodiment 1~9
A kind of modified fibre, specific steps include：
(1) particle diameter of graphene in the first graphene dispersing solution, first graphene dispersing solution is prepared at 0.1~1 μm
Between；The particle diameter of graphene in the second graphene dispersing solution, second graphene dispersing solution is prepared between 1~2 μm；
(2) fiber is taken out into the fiber for being impregnated with the first graphene in the graphene dispersing solution of normal temperature dipping first afterwards, risen
Temperature is to the first temperature, and constant temperature carries out first and post-processed, and obtains the first modified fibre；
(3) the first modified fibre is taken out be impregnated with the second graphene afterwards in the graphene dispersing solution of normal temperature dipping second
Fiber, be warming up to second temperature, constant temperature 30min carries out second and post-processed, and obtains the second modified fibre；
(4) the second modified fibre is cooled down, dried, obtain modified fibre product.
Performance test：Obtained modified fibre is detected according to GB/T 14342-2015 to obtained modified fibre；
Modified fibre is washed 50 times afterwards, continuation is detected according to GB/T 14342-2015 to the modified fibre after washing.
Process conditions and the test result of obtained composite fibre that table 1 gives embodiment 1~9.
Table 1：Embodiment 1~9 prepares the process conditions and test result of modified fibre product
Embodiment 10~13
A kind of modified fibre, the difference with embodiment 7 is, the same time-division in step (2) first graphene dispersing solution
Nano-cellulose (draw ratio 80~120, below diameter 10nm) is dissipated, concentration of the nano-cellulose in dispersion liquid is
0.1wt%, 0.5wt%, 1wt%, 2wt%.
Using performance test methods same as Example 7, test result is shown in Table 2.
Embodiment 14
A kind of modified fibre, the difference with embodiment 3 is that the first and second graphene dispersing solutions are all replaced with into oxidation
Graphene dispersing solution, and reduction step is carried out, it is specially：It is put into hydrazine hydrate reduction liquid in the modified fibre of step (3) second
After row reduction treatment, carry out step (4) and obtain modified fibre product.Using performance test methods same as Example 3, test
It the results are shown in Table 2.
Embodiment 15
A kind of modified fibre, the difference with embodiment 3 is, by the first graphene dispersing solution and the second graphene dispersing solution
All replace with biomass graphene dispersing solution.
Using performance test methods same as Example 3, test result is shown in Table 2.
In addition, the far infrared normal emittance (method of testing FZ/T64010-2000) of the present embodiment fiber reaches 0.9.
Embodiment 16
A kind of modified fibre, specific steps include：
(1) particle diameter of graphene in graphene dispersing solution, the graphene dispersing solution is prepared between 0.1~3 μm；
(2) by polyester fiber impregnated graphite alkene dispersion liquid 10min at room temperature, take out afterwards, in the air for being placed in 95 DEG C
30min, cools down, dries, obtain modified fibre afterwards.
Using performance test methods same as Example 3, test result is shown in Table 2.
Embodiment 17-18
Fiber in embodiment 3 is replaced with into match network compact spinning spun yarn (embodiment 17) and knitting fabric (embodiment
18)。
Table 2 gives the test result for the modified fibre product that embodiment 10~18 is obtained.
Table 2：The test result of the modified fibre product of embodiment 10~18
| Embodiment | Do not wash ratio resistance, Ω cm | Ratio resistance after washing 50 times, Ω cm |
| Embodiment 10 | 1×103 | 1×103 |
| Embodiment 11 | 1×103 | 1×103 |
| Embodiment 12 | 1×103 | 2×103 |
| Embodiment 13 | 7×103 | 8×103 |
| Embodiment 14 | 3×103 | 7×103 |
| Embodiment 15 | 2×103 | 4.8×103 |
| Embodiment 16 | 5.8×104 | 1×105 |
| Embodiment 17 | 3×102 | 5.7×102 |
| Embodiment 18 | 2×102 | 6.2×102 |
In table 2, the yarn of embodiment 17 can be knitted into fabric, detection sheet resistance is carried out using GB12703.4-2010
Rate, the surface resistivity do not washed is 2 × 102Ω, the surface resistivity that washing is 50 times is 7 × 102Ω；The fabric of embodiment 18
Surface resistivity is detected that the surface resistivity do not washed is 2 × 10 using GB12703.4-20102Ω, is washed 50 times
Surface resistivity is 6 × 102Ω。
Comparative example 1
Fiber bodies are modified by a kind of modified fibre by the way of In-situ reaction, are concretely comprised the following steps：
(1) 200g graphenes and 8.52kgPTA, 3.5L ethylene glycol are fed intake mixing, are introduced directly into after ball-milling treatment 20min
To mashing kettle mashing 30min, reacted according to using three kettle PET polymerization techniques, carry out polymerisation, polymerisation is finished
To melt；
(2) melt is in 40 DEG C of cooling waters, and 0.5m/s draft speed condition bottom discharges, directly granulation obtain graphene and be combined
PET master batch；
(3) graphene is combined PET master batch at 110 DEG C, after drum dried 24h, is directly used in melt spinning, spinning goes out
Silk is cooled down using water smoke, 40 DEG C of chilling temperature, 35 DEG C of drying temperature, and melt spinning obtains modified polyester fibre.
Obtained fiber is detected according to GB/T 14342-2015, its ratio resistance do not washed is 1 × 1013Ω·
cm。
Comparative example 2
A kind of modified fibre, is modified by the way of normal temperature dipping, is concretely comprised the following steps：
(1) particle diameter of graphene in graphene dispersing solution, the graphene dispersing solution is prepared between 0.1~3 μm；
(2) polyester fiber is taken out afterwards in 25 DEG C of impregnated graphite alkene dispersion liquid 30min, dries, obtain modified fibre.
Obtained fiber is detected according to GB/T 14342-2015, its ratio resistance do not washed is 1 × 104Ω·
Cm, the ratio resistance after washing 20 times is 1 × 1010Ω·cm。
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of post-processing approach of fibre, it is characterised in that methods described includes：By fibre impregnated graphite alkenes
Be warming up to the elastomeric state temperature of fibrous material after material dispersion liquid, taking-up, and constant temperature carries out Combined Processing, afterwards through supercooling,
Dry, obtain composite fiber product.
2. post-processing approach as claimed in claim 1, it is characterised in that the post-processing temperature is than undulation degree in fibre
The glass transition temperature of material is high more than 5 DEG C；
Preferably, the concentration of the graphite alkenes material dispersion liquid is 0.1~5wt%, preferably 0.3~2wt%；
Preferably, the particle diameter of the graphite alkenes material in the graphite alkenes material dispersion liquid is no more than 20 μm；Preferably
100nm~10 μm, further preferred 200nm~5 μm；
Preferably, the mode of the heating is hot air；
Preferably, the time that the constant temperature carries out Combined Processing is 15~120min；
Preferably, nano-cellulose is added with the graphite alkenes material dispersion liquid；
Preferably, the diameter of the nano-cellulose is not more than 10nm, and draw ratio is not less than 10；
Preferably, concentration of the nano-cellulose in dispersion liquid be below 2wt%, preferably below 1wt%, further preferably
Below 0.5wt%.
3. post-processing approach as claimed in claim 1 or 2, it is characterised in that the graphite alkenes material includes graphene, life
Material graphene, graphene oxide, preferably any a kind or at least two kinds of of mixing of Graphene derivative, graphene and/or life
Material graphene；
Preferably, the Graphene derivative include any a kind in element doping graphene or functional group's graphite alkene thing or
At least two kinds of combinations；
Preferably, when the graphite alkenes material is graphene oxide, reduction treatment is carried out before cooling and/or afterwards；
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process；
Preferably, the reducing agent reducing process is reduced including adding reducing agent；
Preferably, the addition of the reducing agent is the 10~200wt%, preferably 50~100wt% of graphite alkenes material；
Preferably, the reducing agent include ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, Cys, hydroiodic acid or
Any a kind or at least two kinds of of combination in sodium borohydride；
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced；
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reproducibility gas are passed through
Atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
4. the post-processing approach as described in one of claims 1 to 3, it is characterised in that the fibre include fiber precursor,
Any a kind or at least two kinds of of combination in yarn and fabric；
Preferably, the fiber include polyester fiber, nylon fibre, spandex fibre, aramid fiber, acrylic fiber, PVA fibers,
Regenerated celulose fibre.
5. the post-processing approach as described in one of Claims 1 to 4, it is characterised in that the post-processing approach includes following step
Suddenly：
(A1) fibre is impregnated into the first graphite alkenes material dispersion liquid, elastomeric state temperature is warming up to after taking-up, rear
Constant temperature carries out first time Combined Processing under treatment temperature；The grain of graphite alkenes material in the first graphite alkenes material dispersion liquid
Footpath is less than 1 μm；
(A2) fibre after first time Combined Processing is impregnated into the second graphite alkenes material dispersion liquid, heated up after taking-up
To the second post-processing temperature, constant temperature carries out second of Combined Processing, afterwards through supercooling, drying, obtains composite fiber product；
The particle diameter of graphite alkenes material is 1~20 μm in the second graphite alkenes material dispersion liquid.
6. the modified fibre product that a kind of post-processing approach as described in one of Claims 1 to 5 is obtained, it is characterised in that described
The fibrous inside of modified fibre product has outside graphite alkenes material, the fiberoptic fiber of the modified fibre product that there is also stone
Black alkenes material.
7. modified fibre product as claimed in claim 6, it is characterised in that be present in the stone outside the modified fibre product
Black alkenes material is more than being present in graphite alkenes material inside composite fibre；
Preferably, the fibrous inside of the modified fibre product includes crystal region, noncrystalline domain and crystal region and noncrystalline domain
Between gap；
Preferably, there is graphite alkenes material in the fibrous inside crystal region of the modified fibre product, while the modified fibre
There is graphite alkenes material in the fibrous external of product；
Preferably, in the modified fibre product, graphite alkenes material accounts for 0.5~3wt% of modified fibre product；
Preferably, particle diameter≤20 μm of the graphite alkenes material；
Preferably, 1 μm of the particle diameter ＜ for the graphite alkenes material that the fibrous inside of the modified fibre product is present；
Preferably, the particle diameter for the graphite alkenes material that the fibrous external of the modified fibre product is present is 1~20 μm.
8. modified fibre product as claimed in claims 6 or 7, it is characterised in that the fibre includes fiber precursor, yarn
Line and fabric；
When the graphite alkenes material is graphene and/or biomass graphene, the modified fibre product fibrous material
Ratio resistance≤1 × 105Ω；
Preferably, when the graphite alkenes material is graphene and/or biomass graphene, the modified fibre product washing
After 50 times, ratio resistance≤1 × 10 of its fibrous material5Ω；
Preferably, the modified fibre product includes modified fibre, the yarn comprising modified fibre and knitting comprising modified fibre
Any a kind or at least two kinds of of combination in thing；
Preferably, the modified fibre includes modified polyester fibre, modified nylon fiber, modified spandex fibre, modifying aramid fiber fibre
Dimension, modified acrylic fibres, modified PVA fiber, modification regeneration cellulose fibre；
Preferably, the yarn comprising modified fibre is spun by the modified fibre list, blending or obtained with unmodified fibers blending
Arrive；
Preferably, the fabric comprising modified fibre is made up of the modified fibre and the yarn comprising modified fibre.
9. the modified fibre product as described in one of claim 6~8, it is characterised in that be combined in the modified fibre product
There is nano-cellulose；
Preferably, the nano-cellulose is wrapped in the modified fibre product internally and/or externally.
10. a kind of purposes of the modified fibre product as described in one of claim 6~9, it is characterised in that the modified fibre system
Product are used to prepare home textile, underwear, protective garment, thermal cloth, socks.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710197196.1A CN106948171B (en) | 2017-03-29 | 2017-03-29 | Post-treatment method of fiber product, obtained modified fiber product and application thereof |
| KR1020197030234A KR20190125480A (en) | 2017-03-15 | 2018-03-14 | Modified textile products, manufacturing methods and uses thereof |
| DE112018001356.1T DE112018001356T5 (en) | 2017-03-15 | 2018-03-14 | Modified fiber product, manufacturing method thereof and use thereof |
| JP2019572277A JP6852200B2 (en) | 2017-03-15 | 2018-03-14 | Modified textile products, preparation methods and their use |
| PCT/CN2018/079035 WO2018166477A1 (en) | 2017-03-15 | 2018-03-14 | Modified fibre product, preparation method therefor and use thereof |
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| CN201710197196.1A CN106948171B (en) | 2017-03-29 | 2017-03-29 | Post-treatment method of fiber product, obtained modified fiber product and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106948170A (en) * | 2017-03-29 | 2017-07-14 | 山东圣泉新材料股份有限公司 | A kind of post-processing approach of fibre, obtained modified fibre product and application thereof |
| CN107245879A (en) * | 2017-06-13 | 2017-10-13 | 山东圣泉新材料股份有限公司 | A kind of modified polyester fibre product, preparation method and its usage |
| CN108095207A (en) * | 2017-12-28 | 2018-06-01 | 武汉猫人制衣有限公司 | A kind of composition and its application in thermal underwear face fabric |
| WO2018166477A1 (en) * | 2017-03-15 | 2018-09-20 | 山东圣泉新材料股份有限公司 | Modified fibre product, preparation method therefor and use thereof |
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| CN115821573A (en) * | 2021-09-16 | 2023-03-21 | 中国石油化工股份有限公司 | Conductive dry acrylic fiber and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105484016A (en) * | 2015-12-28 | 2016-04-13 | 宁国市龙晟柔性储能材料科技有限公司 | Preparation method of graphene composite conductive fiber |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106283610A (en) * | 2016-08-04 | 2017-01-04 | 武汉纺织大学 | A kind of Graphene inductive formation polypyrrole nano line conducing composite material preparation method |
| CN106400471A (en) * | 2016-12-01 | 2017-02-15 | 西南大学 | Preparation method of nano carboxylation graphene compound polyester conductive textile fabric |
| CN106521744A (en) * | 2016-11-03 | 2017-03-22 | 武汉纺织大学 | Conductive elastic composite yarn of reduced oxidized graphene and preparation method of yarn |
| CN106948170A (en) * | 2017-03-29 | 2017-07-14 | 山东圣泉新材料股份有限公司 | A kind of post-processing approach of fibre, obtained modified fibre product and application thereof |
-
2017
- 2017-03-29 CN CN201710197196.1A patent/CN106948171B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105484016A (en) * | 2015-12-28 | 2016-04-13 | 宁国市龙晟柔性储能材料科技有限公司 | Preparation method of graphene composite conductive fiber |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106283610A (en) * | 2016-08-04 | 2017-01-04 | 武汉纺织大学 | A kind of Graphene inductive formation polypyrrole nano line conducing composite material preparation method |
| CN106521744A (en) * | 2016-11-03 | 2017-03-22 | 武汉纺织大学 | Conductive elastic composite yarn of reduced oxidized graphene and preparation method of yarn |
| CN106400471A (en) * | 2016-12-01 | 2017-02-15 | 西南大学 | Preparation method of nano carboxylation graphene compound polyester conductive textile fabric |
| CN106948170A (en) * | 2017-03-29 | 2017-07-14 | 山东圣泉新材料股份有限公司 | A kind of post-processing approach of fibre, obtained modified fibre product and application thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018166477A1 (en) * | 2017-03-15 | 2018-09-20 | 山东圣泉新材料股份有限公司 | Modified fibre product, preparation method therefor and use thereof |
| CN106948170A (en) * | 2017-03-29 | 2017-07-14 | 山东圣泉新材料股份有限公司 | A kind of post-processing approach of fibre, obtained modified fibre product and application thereof |
| CN106948170B (en) * | 2017-03-29 | 2020-08-11 | 山东圣泉新材料股份有限公司 | Post-treatment method of fiber product, obtained modified fiber product and application thereof |
| CN107245879A (en) * | 2017-06-13 | 2017-10-13 | 山东圣泉新材料股份有限公司 | A kind of modified polyester fibre product, preparation method and its usage |
| CN108095207A (en) * | 2017-12-28 | 2018-06-01 | 武汉猫人制衣有限公司 | A kind of composition and its application in thermal underwear face fabric |
| CN109137478A (en) * | 2018-07-02 | 2019-01-04 | 张家港锦亿化纤有限公司 | A kind of production method of conductive dacron fibre |
| CN110328834A (en) * | 2019-06-28 | 2019-10-15 | 燕山大学 | A kind of forming and machining method of crystallinity CFRTP |
| CN110328834B (en) * | 2019-06-28 | 2020-04-21 | 燕山大学 | Forming processing method of crystalline CFRTP |
| CN112796101A (en) * | 2021-02-04 | 2021-05-14 | 中国矿业大学(北京) | Composite fiber and preparation method thereof, and graphene flexible temperature sensing array and preparation method thereof |
| CN112796101B (en) * | 2021-02-04 | 2021-12-28 | 中国矿业大学(北京) | Composite fiber and preparation method thereof, and graphene flexible temperature sensing array and preparation method thereof |
| CN115821573A (en) * | 2021-09-16 | 2023-03-21 | 中国石油化工股份有限公司 | Conductive dry acrylic fiber and preparation method thereof |
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