CN107254774A - A kind of modified nylon fibre, preparation method and its usage - Google Patents
A kind of modified nylon fibre, preparation method and its usage Download PDFInfo
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- CN107254774A CN107254774A CN201710443948.8A CN201710443948A CN107254774A CN 107254774 A CN107254774 A CN 107254774A CN 201710443948 A CN201710443948 A CN 201710443948A CN 107254774 A CN107254774 A CN 107254774A
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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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- 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
- D06M11/76—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 oxides or carbonates
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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
- 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
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of modified nylon fibre, the nylon fibre of the modified nylon fibre is inside and outside to have graphene sheet layer；The nylon fibre product includes nylon fibre, polyamide fibre yarn and nylon fabric.The present invention in the inside and outside attachment of nylon fibre or doses graphene simultaneously, adds the uniformity and fastness of graphene presence；The present invention improves the electric conductivity of nylon fibre by adding graphene and/or biomass graphene；Addition graphene oxide and/or biomass graphene further enhancing the far infrared performance of nylon fibre；The preparation method that the present invention is provided effectively can dose graphene to nylon fibre, while the coated graphite alkene lamella outside nylon fibre, graphene being uniformly distributed on nylon fibre is realized by nylon fibre article impregnation graphene solution.
Description
Technical field
The invention belongs to fibre preparation field, and in particular to a kind of modified nylon fibre, preparation method and its
Purposes, more particularly to a kind of conductive modified nylon fibre, preparation method and its usage.
Background technology
The development of conductive fiber start from the 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 compound firmness of fibre graphene prepared by single impregnation technology is not strong enough, 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.
Polyamide fibre, scientific name Silon is commonly called as nylon (Nylon), and English name Polyamide (PA), intensity is high, wear-resisting
Property it is good, resilience is good, can with it is pure spinning and blending make various dress materials and knitwear, it is to contain recurring amide radical on molecular backbone
The general name of the thermoplastic resin of group-[NHCO]-.
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, the adhesion-tight degree of graphene is further ensured, makes its function
Do not decay significantly because of increasing for washing times.
This area needs to develop a kind of modified fibre product, itself and graphite alkenes Material cladding, can improve the fiber
The performances such as the electric conductivity or far infrared of product, while being ensured of the adhesion-tight degree of graphene.
The content of the invention
It is an object of the invention to provide a kind of modified nylon fibre, the polyamide fibre of the modified nylon fibre is fine
Dimension is inside and outside to have graphene sheet layer；The nylon fibre product includes nylon fibre, polyamide fibre yarn and nylon fabric.
The present invention passes through inside and outside while setting graphene sheet layer in nylon fibre, it is possible to increase graphene sheet layer exists
Fastness on nylon fibre, while improving branch uniformity of the graphene in nylon fibre radial direction.
Exemplarily, the yarn of the present invention comprising modified nylon fiber is spun by the modified nylon fiber list, blending
Or obtained with unmodified nylon fibre blending.The fabric comprising modified nylon fiber is described by the modified nylon fiber
Yarn comprising modified nylon fiber is made.
Preferably, in modified nylon fiber of the present invention, it is present in the graphene film of the modified nylon fibrous external
Layer is more than the graphene sheet layer for being present in modified nylon fibrous inside.The modified nylon fibrous external has more graphene
Lamella, can overlap in the outside of modified nylon fiber, preferably improve the conduction of the modified nylon fibre
Property.
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, graphene sheet layer gross mass is total no more than modified nylon fibre in the modified nylon fibre
0.5~3wt% of quality.Graphene sheet layer content should not be excessive, is excessively easily caused the reduction of modified nylon fibre strength, resource
Waste.
In the present invention, crystal region, noncrystalline domain and the crystal region of the modified nylon fibrous inside including fiber with
Gap between noncrystalline domain.
Gap of the present invention, space, hole can be replaced mutually, represent the space of fibrous inside.
Preferably, there is graphene sheet layer in the modified nylon fibrous inside crystal region, while the modified nylon fiber
There is graphene sheet layer in outside.
Preferably, particle diameter≤20 μm of the graphene sheet layer, such as 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μ
M, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm etc..
Preferably, the particle diameter for the graphene sheet layer that the modified nylon fibrous inside is present is less than 1 μm, 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 graphene sheet layer that the modified nylon fibrous external is present is 1~20 μm, such as 1 μm, 2 μ
M, 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..
In a detailed embodiment, modified nylon fibre of the present invention contains modified nylon fiber, described
There is graphene sheet layer in modified nylon fibrous inside crystal region, there is also graphene sheet layer for the modified nylon fibrous external.
Preferably, in the modified nylon fibre modified nylon fiber ratio resistance≤1 × 105Ω cm, such as 1
×104Ω·cm、4×104Ω·cm、7×104Ω·cm、9×104Ω·cm、1×103Ω·cm、5×103Ω·cm、8
×103Ω·cm、1×102Ω cm, 1 × 10 Ω cm etc..
Preferably, in the modified nylon fibre after modified nylon fiber washing 50 times, its ratio resistance≤1 ×
105Ω cm, such as 1 × 104Ω·cm、4×104Ω·cm、7×104Ω·cm、9×104Ω·cm、1×103Ω·cm、
5×103Ω·cm、8×103Ω·cm、1×102Ω cm, 1 × 10 Ω cm etc..
Preferably, when the graphene sheet layer is graphene oxide and/or biomass graphene, the nylon fibre system
After product are washed 50 times, its far infrared normal emittance is not less than 0.85, for example, be not less than 0.87, be not less than 0.88, be not less than
0.90。
In order to further improve the intensity of the modified nylon fibre and the fastness of graphene sheet layer, described changes
Contain nano-cellulose in property nylon fibre product.The addition of appropriate nano-cellulose can improve and wind graphene sheet layer
On the nylon fibre, and the winding of nano-cellulose can improve the intensity of the modified nylon fibre.
Preferably, it is compounded with nano-cellulose in the modified nylon fiber of the modified nylon fibre.
Preferably, the nano-cellulose is wrapped in the modified nylon fiber internally and/or externally.Refer specifically to, receive
Rice cellulose is by high draw ratio and small diameter, by outside graphene sheet layer and fibrous inside crystal region or fibrous inside stone
Black alkene lamella is bundled or overlapped so that outside graphene sheet layer is difficult for drop-off.
The two of the object of the invention are to provide a kind of preparation method of the modified nylon fibre as described in the first purpose, institute
Stating method includes impregnating unmodified nylon fibre product in graphene sheet layer dispersion liquid, afterwards through supercooling, drying, obtains
Modified nylon fibre after to processing；Wherein, the temperature of the dipping is bright and beautiful to be less than more than the glass transition temperature of polyamide fibre
The glutinous stream temperature of synthetic fibre, the temperature of preferably described dipping is 45~80 DEG C.
By unmodified nylon fibre article impregnation in the glass transition temperature more than polyamide fibre and less than glutinous stream temperature, such as 45
In~80 DEG C of dispersion liquid, the dipping temperature of the dispersion liquid is in again between glassy state temperature and elastomeric state temperature, and described 45
~80 DEG C can improve the motion of macromolecular in the fiber so that crystal region is converted to noncrystalline domain so that noncrystalline domain
Space becomes big so that the space between crystal region and noncrystalline domain between the macromolecular in region becomes big；It is dispersed in graphite alkenes simultaneously
The particle of graphene sheet layer in dispersion liquid enters described space；Then impregnated fiber cooling so that in dipping process
Graphene into the space is fixed on fibrous inside, and because the larger graphene sheet layer being blocked in outside space of particle diameter
Understand to coat, fit, or even can be partly to enter fibrous inside, partly the form positioned at fibrous external is present.
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 modified nylon fibre include modified nylon fiber, the yarn comprising modified nylon fiber and
Any a kind or at least two kinds of of combination in fabric comprising modified nylon fiber.Furtherly, modified nylon fibre can
Can be yarn or fabric to be fiber；It can be fiber impregnation graphene solution, can be yarn dipping stone
Black alkene solution, can be fabric impregnated graphite alkene solution.
Preferably, the graphene sheet layer includes graphene, biomass graphene, graphene oxide, Graphene derivative
Any a kind or at least two kinds of of mixing, preferably graphene, biomass graphene and/or graphene oxide.
Preferably, the graphene sheet layer include graphene, graphene oxide, any a kind of Graphene derivative or extremely
Few 2 kinds mixing.
Preferably, graphene is prepared including graphite by stripping method, and graphene oxide is prepared by reduction, stone
Ink is prepared by redox, and carbonaceous gas is prepared by CVD, and high-temperature cracking method is passed through by raw material of biomass
Prepare.
Preferably, the graphene oxide includes the graphene that TEMPO systems are aoxidized.
The graphene of TEMPO systems oxidation can insert oxidisability functional group inside graphene, improve graphene oxide
Dispersing uniformity in dispersion liquid, reduces the reunion of graphene in graphene dispersing solution, improves the utilization rate of graphene.
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.
Preferably, the concentration of the graphene sheet layer 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..
Preferably, the particle diameter of the graphene sheet layer in the graphene sheet layer dispersion liquid is no more than 20 μm, is preferably
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..
Preferably, the dip time be 15~120min, such as 16min, 19min, 23min, 26min, 32min,
55min, 66min, 73min, 78min, 85min, 88min, 95min etc..
Graphene oxide electric conductivity itself is poor, in order to ensure the conduction for the fibre being modified by graphene oxide
Property, the present invention can carry out reduction treatment to the modified fibre product for being compounded with graphene oxide.
Preferably, when the graphene sheet layer includes graphene oxide, also original place is carried out before cooling and/or afterwards
Reason.
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 graphene sheet layer.
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.
Preferably, nano-cellulose is added with the graphene sheet layer dispersion liquid.
Preferably, the diameter of the nano-cellulose is not more than 10nm, and draw ratio is not less than 10, and draw ratio can be 20,
30,50,100 etc..
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 can circumferentially be wound in fibrous external, 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 graphene sheet layer on fiber.But nano-cellulose is non-conductive in itself, excessively
Nano-cellulose can cause the decline of electric conductivity.
As optional technical scheme, described impregnate unmodified nylon fibre product in graphene sheet layer dispersion liquid is divided
Two steps are carried out, and specifically include following steps：
(A1) by unmodified nylon fibre article impregnation into the first graphene sheet layer dispersion liquid, the first dipping polyamide fibre is obtained
Fibre；The particle diameter of graphene sheet layer is less than 1 μm in the first graphene sheet layer dispersion liquid；
(A2) the first dipping nylon fibre article impregnation is obtained into the second dipping brocade into the second graphene sheet layer dispersion liquid
Synthetic fibre fibre；The particle diameter of graphene sheet layer is 1~20 μm in the second graphene sheet layer dispersion liquid.
The step (A1) and (A2) dipping temperature are the glass transition temperature more than polyamide fibre and flow temperature, preferably 45 less than glutinous
~80 DEG C, and the step (A2) dipping temperature is less than step (A1) dipping temperature.
Because the size of nylon fibre internal voids is limited, step (A1) is less than 1 μm of graphene sheet layer only with particle diameter
Nylon fibre product is modified, it is well known that graphene particle diameter is smaller to be less susceptible to disperse, it is easier to reunite therefore past
Toward the graphene solution of selection low concentration, the consumption of graphene is so also saved, and reduces big particle diameter graphene sheet layer and is blocked up
The probability in space is filled in, the adhesion amount of graphene is improved.It is 1~20 μm of graphene sheet layer to fiber that step (A2), which uses particle diameter,
Product is modified, and big particle diameter graphene sheet layer can be made to be present in fibrous external in the way of coating, fit, stone is more beneficial for
Black alkene forms conductive network outside nylon fibre, additionally it is possible to play a part of closing fibrous inside space, by increasing capacitance it is possible to increase graphite
The fastness of alkene lamella in the fibre.
The three of the object of the invention are to provide a kind of purposes of the modified nylon fibre as described in the first purpose, the modification
Nylon 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) present invention in the inside and outside attachment of nylon fibre or doses graphene simultaneously, adds graphene presence
Uniformity and fastness；
(2) present invention improves the electric conductivity of nylon fibre by adding graphene and/or biomass graphene；Addition
Graphene oxide and/or biomass graphene further enhancing the far infrared performance of nylon fibre；
(3) preparation method that the present invention is provided effectively can dose graphene to nylon fibre, while in brocade
Synthetic fibre fibrous external coated graphite alkene lamella, realizes graphene on nylon fibre by nylon fibre article impregnation graphene solution
Be uniformly distributed.
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 1~7
A kind of modified nylon fiber, specific steps include：
(1) particle diameter for preparing graphene in the first graphene dispersing solution, first graphene dispersing solution is less than 1 μm；Match somebody with somebody
The particle diameter of graphene in the second graphene dispersing solution, second graphene dispersing solution is made between 1~2 μm；
(2) nylon fibre is impregnated into the first graphene dispersing solution in the first temperature, takes out be impregnated with the first graphene afterwards
Nylon fibre, and continued to be immersed in the second graphene dispersing solution and impregnate 30min, taken out afterwards, dry, be modified
Nylon fibre.
Performance test：By obtained modified nylon fiber according to GB/T 14342-2015 to obtained modified nylon fiber
Detected；Afterwards by modified nylon fiber washing 50 times, continue according to GB/T 14342-2015 to the modified nylon after washing
Fiber is detected.
Table 1 gives the process conditions of embodiment 1~8 and the test result of obtained modified nylon fiber.
Table 1：Embodiment 1~8 prepares the process conditions and test result of modified nylon fiber
It can be seen from Table 1 that, when the dipping temperature of embodiment 7 first is less than the second dipping temperature, due to double-steeping
When fiber polymer motion ratio impregnate violent for the first time, cause the graphene for being immersed in fibrous inside for the first time to overflow, hinder simultaneously
Hinder second of dipping effect so that ratio resistance is raised；When graphene particle diameter is more than the second maceration extract in the maceration extract of embodiment 8 first
Graphene particle diameter when so that fibrous inside graphene content is relatively low, and outside content is higher, it is inside and outside between do not form stronger
Active force, cause washing times increase graphene come off it is more obvious.
Embodiment 9~12
A kind of modified fibre, the difference with embodiment 3 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% (embodiment 9), 0.5wt% (embodiment 10), 1wt% (embodiment 11), 2wt% (embodiment 12).
Using performance test methods same as Example 3, test result is shown in Table 2.
Embodiment 13
A kind of modified nylon fiber, the difference with embodiment 3 is, the first and second graphene dispersing solutions are all replaced with
Graphene oxide dispersion, and reduction step is carried out, it is specially：In step 2) take out the nylon fibre that dipping has impregnated for the second time
After be put into hydrazine hydrate reduction liquid carry out reduction treatment after, dry, obtain modified nylon fiber.Using same as Example 3
Performance test methods, test result is shown in Table 2.
Embodiment 14
A kind of modified nylon fiber, the difference with embodiment 3 is, the first and second graphene dispersing solutions are all replaced
For 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 modified nylon fiber reaches
To 0.9.
Embodiment 15
A kind of modified nylon fiber, specific steps include：
(1) particle diameter of graphene in graphene dispersing solution, the graphene dispersing solution is prepared between 0.1~3 μm；
(2) nylon fibre is taken out afterwards in 95 DEG C of impregnated graphite alkene dispersion liquid 30min, dries, obtain modified fibre.
Using performance test methods same as Example 4, test result is shown in Table 2.
Embodiment 16~17
Nylon fibre in embodiment 3 is replaced with into the yarn (embodiment 16) that match network compact spinning is spun into, and knitting fabric
(embodiment 17).
Table 2 gives the test result for the modified fibre product that embodiment 9~17 is obtained.
Table 2：The test result of the modified fibre product of embodiment 9~17
| Embodiment | Do not wash ratio resistance, Ω cm | Ratio resistance after washing 50 times, Ω cm |
| Embodiment 9 | 1×102 | 1×102 |
| Embodiment 10 | 1×102 | 1×102 |
| Embodiment 11 | 1×102 | 2×102 |
| Embodiment 12 | 8×103 | 9×103 |
| Embodiment 13 | 3×102 | 8×102 |
| Embodiment 14 | 2×102 | 5×102 |
| Embodiment 15 | 6×104 | 1×105 |
| Embodiment 16 | 3×102 | 6×102 |
| Embodiment 17 | 2×102 | 6×102 |
In table 2, the yarn of embodiment 16 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 17
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
A kind of modified nylon fiber, is concretely comprised the following steps：
(1) 200g graphenes and 2kg slices of caprone melt pelletizations are obtained into graphene and is combined PA master batches；
(2) after the compound PA master batches of above-mentioned graphene are mixed with 13kg slices of caprone, it is fine that melt spinning obtains modified nylon
Dimension.
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 nylon fiber, is modified by the way of normal temperature dipping, 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) nylon fibre is taken out afterwards in 25 DEG C of impregnated graphite alkene dispersion liquid 30min, dried, obtain modified nylon fine
Dimension.
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 (9)
1. a kind of modified nylon fibre, it is characterised in that inside the nylon fibre of the modified nylon fibre and outer
There is graphene sheet layer in portion；
The nylon fibre product includes nylon fibre, polyamide fibre yarn or nylon fabric.
2. modified nylon fibre as claimed in claim 1, it is characterised in that be present in the stone outside the nylon fibre
Black alkene lamella is more than the graphene sheet layer being present in inside nylon fibre；
Preferably, the gross mass of graphene sheet layer is modified nylon fibre gross mass in the modified nylon fibre
0.5~3wt%；
Preferably, the modified nylon fibrous inside includes crystal region, noncrystalline domain and crystal region and the noncrystalline domain of fiber
Between gap；
Preferably, there is graphene sheet layer in the modified nylon fibrous inside crystal region, while the modified nylon fibrous external
There is graphene sheet layer；
Preferably, particle diameter≤20 μm of the graphene sheet layer；
Preferably, the particle diameter for the graphene sheet layer that the modified nylon fibrous inside is present is less than 1 μm；
Preferably, the particle diameter for the graphene sheet layer that the modified nylon fibrous external is present is 1~20 μm.
3. modified nylon fibre as claimed in claim 1 or 2, it is characterised in that in the modified nylon fibre
Ratio resistance≤1 × 10 of nylon fibre5Ω·cm；
Preferably, after the modified nylon fibre is washed 50 times, ratio resistance≤1 × 10 of modified nylon fiber5Ω·
cm。
4. the modified nylon fibre as described in one of claims 1 to 3, it is characterised in that the modified nylon fiber system
Nano-cellulose is compounded with the nylon fibre of product；
Preferably, the nano-cellulose is wrapped in the nylon fibre internally and/or externally.
5. the preparation method of a kind of modified nylon fibre as described in one of Claims 1 to 4, it is characterised in that described
Method includes impregnating unmodified nylon fibre product in graphene sheet layer dispersion liquid, afterwards through supercooling, drying, obtains
Modified nylon fibre after processing；
Wherein, the temperature of the dipping is glutinous stream temperature of the glass transition temperature less than polyamide fibre more than polyamide fibre；
Preferably, the temperature of the dipping is 45~80 DEG C.
6. preparation method as claimed in claim 5, it is characterised in that the graphene sheet layer includes graphene, graphite oxide
Any a kind or at least two kinds of of mixing of alkene, Graphene derivative；
Preferably, graphene is prepared including graphite by stripping method, graphene oxide is prepared by reduction, graphite leads to
Oxidization-reduction is prepared, carbonaceous gas is prepared by CVD, prepared by raw material of biomass by high-temperature cracking method
Any a kind or at least two kinds of of combination in obtaining；
Preferably, the concentration of the graphene sheet layer dispersion liquid is 0.1~5wt%, preferably 0.3~2wt%；
Preferably, the particle diameter of the graphene sheet layer in the graphene sheet layer dispersion liquid is no more than 20 μm；Preferably 100nm~
10 μm, further preferred 200nm~5 μm；
Preferably, the dip time is 15~120min；
Preferably, when the graphene sheet layer includes 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 graphene sheet layer；
Preferably, the reducing agent includes ascorbic acid, hydrazine hydrate, glucose, ethylenediamine, sodium citrate, Cys, hydrogen
Any a kind or at least two kinds of of combination in acid iodide 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 reproducibility gas are passed through
Atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
7. the preparation method as described in claim 5 or 6, it is characterised in that be added with and receive in the graphene sheet layer dispersion liquid
Rice cellulose；
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 the graphene sheet layer dispersion liquid is below 2wt%, preferably 1wt%
Hereinafter, further preferably below 0.5wt%.
8. the preparation method as described in one of claim 5~7, it is characterised in that by the unmodified nylon fibre product
Impregnate and be carried out in two steps in graphene sheet layer dispersion liquid, specifically include following steps：
(A1) by unmodified nylon fibre article impregnation into the first graphene sheet layer dispersion liquid, the first dipping nylon fibre is obtained
Product；The particle diameter of graphene sheet layer is less than 1 μm in the first graphene sheet layer dispersion liquid；
(A2) the first dipping nylon fibre article impregnation is obtained into the second dipping polyamide fibre fine into the second graphene sheet layer dispersion liquid
Fiber products；The particle diameter of graphene sheet layer is 1~20 μm in the second graphene sheet layer dispersion liquid；
Preferably, the step (A1) and (A2) dipping temperature are glutinous stream temperature of the glass transition temperature less than polyamide fibre more than polyamide fibre
Degree, preferably 45~80 DEG C, and the step (A2) dipping temperature is less than step (A1) dipping temperature.
9. a kind of purposes of the modified nylon fibre as described in one of Claims 1 to 4, it is characterised in that the modified brocade
Synthetic fibre fibre is used to prepare home textile, underwear, protective garment, thermal cloth, socks.
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| CN201710443948.8A CN107254774A (en) | 2017-06-13 | 2017-06-13 | A kind of modified nylon fibre, preparation method and its usage |
| KR1020197030234A KR20190125480A (en) | 2017-03-15 | 2018-03-14 | Modified textile products, manufacturing methods and uses thereof |
| PCT/CN2018/079035 WO2018166477A1 (en) | 2017-03-15 | 2018-03-14 | Modified fibre product, preparation method therefor and use thereof |
| JP2019572277A JP6852200B2 (en) | 2017-03-15 | 2018-03-14 | Modified textile products, preparation methods and their use |
| DE112018001356.1T DE112018001356T5 (en) | 2017-03-15 | 2018-03-14 | Modified fiber product, manufacturing method thereof and use thereof |
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| CN108893975A (en) * | 2018-07-30 | 2018-11-27 | 嘉兴学院 | A kind of method that graphene is used for the arrangement of polyamide fibre product |
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