CN107245878A - A kind of modified acrylic fibres product, preparation method and its usage - Google Patents
A kind of modified acrylic fibres product, preparation method and its usage Download PDFInfo
- Publication number
- CN107245878A CN107245878A CN201710443946.9A CN201710443946A CN107245878A CN 107245878 A CN107245878 A CN 107245878A CN 201710443946 A CN201710443946 A CN 201710443946A CN 107245878 A CN107245878 A CN 107245878A
- Authority
- CN
- China
- Prior art keywords
- graphene
- sheet layer
- graphene sheet
- acrylic
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of modified acrylic fibres product, the acrylic fiber of the modified acrylic fibres product is inside and outside to have graphene sheet layer；The acrylic fiber product includes acrylic fiber, Acrylic Fiber or acrylic fabric.The present invention in the inside and outside attachment of acrylic fiber or doses graphene simultaneously, adds the uniformity and fastness of graphene presence；The present invention improves the electric conductivity of acrylic fiber by adding graphene and/or biomass graphene；Addition graphene oxide and/or biomass graphene further enhancing the far infrared performance of acrylic fiber；The preparation method that the present invention is provided effectively can dose graphene to acrylic fiber, while the coated graphite alkene lamella outside acrylic fiber, graphene being uniformly distributed on acrylic fiber is realized by acrylic fiber article impregnation graphene solution.
Description
Technical field
The invention belongs to fibre preparation field, and in particular to a kind of modified acrylic fibres product, preparation method and its
Purposes, more particularly to a kind of conductive modified acrylic fibres product, 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.
Acrylic fibers refer generally to polyacrylonitrile fibre, and polyacrylonitrile or acrylonitrile content are more than the propylene of 85% (mass percent)
The synthetic fibers that lonitrile copolymer is made.The performance pole of polyacrylonitrile fibre is like wool, and preferably, during elongation 20% rebound degree is still for elasticity
Can keep 65%, fluffy curling and it is soft, warmth retention property is higher than wool by 15%, the title for having synthetic wool.
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 acrylic fibres product, the acrylic fibers of the modified acrylic fibres product are fine
Dimension is inside and outside to have graphene sheet layer；The acrylic fiber product includes acrylic fiber, Acrylic Fiber or acrylic fabric.
The present invention passes through in fibrous inside and outside setting graphene sheet layer simultaneously, it is possible to increase graphene sheet layer is in fiber
On fastness, while improve graphene fiber radial direction branch's uniformity.
Exemplarily, it is of the present invention to be spun comprising modified acrylic fibers yarn by the modified acrylic fibres list, blending or with not
Modified acrylic fibres blending is obtained.The fabric comprising modified acrylic fibres is by the modified acrylic fibres, and described include changes
The yarn of property acrylic fiber is made.
Preferably, in modified fibre of the present invention, it is present in the graphene sheet layer ratio outside the modified acrylic fibres
The graphene sheet layer being present in inside modified acrylic fibres is more.There is more graphene film outside the modified acrylic fibres
Layer, can overlap in the outside of modified acrylic fibres, preferably improve the electric conductivity of the modified acrylic fibres 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, graphene sheet layer gross mass is modified acrylic fibres product gross mass in the modified acrylic fibres product
0.5~3wt%.Graphene sheet layer content should not be excessive, is excessively easily caused fibre strength reduction, the wasting of resources.
In the present invention, crystal region, noncrystalline domain and the crystallization of modified fibre are included inside the modified acrylic fibres
Gap between area and 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 acrylic fibres internal junction crystalline region, while the modified acrylic fibres
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 of the graphene sheet layer existed inside the modified acrylic fibres 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 of the graphene sheet layer existed outside the modified acrylic fibres 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 fibre product of the present invention contains modified fibre, the modified fibre
Internal junction crystalline region has outside graphene sheet layer, the modified fibre that there is also graphene sheet layer.
Preferably, in the modified fibre product modified fibre 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, after modified fibre is washed 50 times in the modified fibre product, 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 fibre water
Wash after 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 fibre product and the fastness of graphene sheet layer, described is modified fine
Contain nano-cellulose in fiber products.The addition of appropriate nano-cellulose can be improved is wrapped in the fibre by graphene sheet layer
In dimension, 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 acrylic fibres 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 graphene sheet layer and fibrous inside crystal region or fibrous inside graphene
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 acrylic fibres product as described in the first purpose, institute
Stating method includes impregnating unmodified acrylic fiber product in graphene sheet layer dispersion liquid, afterwards through supercooling, drying, obtains
Modified acrylic fibres product after to processing；Wherein, the temperature of the dipping is more than the glass transition temperature of acrylic fibers less than acrylic fibers
Glutinous stream temperature, preferably 80~100 DEG C.
Unmodified fibre is immersed in glutinous stream temperature of the glass transition temperature less than acrylic fibers more than acrylic fibers, such as 80
In~100 DEG C of dispersion liquid, the dipping temperature of the dispersion liquid is between glass transition temperature and elastomeric state temperature, when temperature reaches
Glass transition temperature Tg to the acrylic fibers can improve the motion of macromolecular in acrylic fiber so that crystal region turns to noncrystalline domain
Change so that the space of noncrystalline domain becomes big so that the space between crystal region and noncrystalline domain between the macromolecular in region becomes big；Together
When be dispersed in the particle of graphene sheet layer in graphene sheet layer dispersion liquid and enter described space；Subsequent impregnated fiber is cold
But so that the graphene in dipping process into the space is fixed on fibrous inside, and is blocked in sky because particle diameter is larger
Graphene sheet layer outside gap can to coat, laminating, or even can be partly to enter fibrous inside, partly positioned at the shape of fibrous external
Formula 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 acrylic fibres product include modified acrylic fibres, the yarn comprising modified fibre and comprising
Any a kind or at least two kinds of of combination in the fabric of modified fibre.Furtherly, fibre can be fiber, can be yarn
Line or fabric；It can be fiber impregnation graphene solution, can be yarn impregnated graphite alkene solution, can be face
Expect 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.
It is described to impregnate unmodified fibre in two steps in graphene sheet layer dispersion liquid as optional technical scheme
Carry out, specifically include following steps：
(A1) by unmodified fibers article impregnation into the first graphene sheet layer dispersion liquid, the first dipping acrylic fiber 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 acrylic fiber article impregnation is obtained into the second dipping nitrile 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.
Wherein, the temperature of the dipping is more than glutinous stream temperature of the glass transition temperature less than acrylic fibers of acrylic fibers, preferably 80~100
DEG C, and the step (A2) dipping temperature is less than step (A1) dipping temperature.
Because the size of acrylic fiber internal voids is limited, step (A1) is less than 1 μm of graphene sheet layer only with particle diameter
Fibre is modified, it is well known that graphene particle diameter is smaller to be less susceptible to disperse, it is easier to reunite, therefore often select
The graphene solution of low concentration is selected, the consumption of graphene is so also saved, and reduces big particle diameter graphene sheet layer and blocks empty
The probability of gap, improves the adhesion amount of graphene.It is 1~20 μm of graphene sheet layer to acrylic 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 acrylic fiber, 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 acrylic fibres product as described in the first purpose, the modification
Acrylic fiber 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 acrylic fiber or doses graphene simultaneously, adds graphene presence
Uniformity and fastness；
(2) present invention improves the electric conductivity of acrylic fiber by adding graphene and/or biomass graphene；Addition
Graphene oxide and/or biomass graphene further enhancing the far infrared performance of acrylic fiber；
(3) preparation method that the present invention is provided effectively can dose graphene to acrylic fiber, while in nitrile
Synthetic fibre fibrous external coated graphite alkene lamella, realizes graphene on acrylic fiber by acrylic fiber 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 1~8
A kind of modified acrylic fibres, 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) fiber is impregnated into the first graphene dispersing solution in the first temperature, the nitrile for being impregnated with the first graphene is taken out afterwards
Synthetic fibre fiber, and continued to be immersed in the second graphene dispersing solution and impregnate 30min, take out afterwards, dry, obtain modifying orlon
Fiber.
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 modified fibre that table 1 gives embodiment 1~8.
Table 1：Embodiment 1~8 prepares the process conditions of modified fibre and the test result of the modified fibre
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 fibre, the difference with embodiment 3 is, 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：In step 2) take out the fiber that has impregnated for the second time of dipping after be put into water
Close in hydrazine reducing solution and carry out after reduction treatment, dry, obtain modified fibre.Using performance test methods same as Example 3,
Test result is shown in Table 2.
Embodiment 14
A kind of modified fibre, the difference with embodiment 3 is, the first and second graphene dispersing solutions are all replaced and made a living
Material 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 15
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) polyester fiber 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
Fiber in embodiment 3 is replaced with into the yarn (embodiment 16) that match network compact spinning is spun into, and knitting fabric (is implemented
Example 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 | 7×104 | 2×105 |
| Embodiment 16 | 4×102 | 6×102 |
| Embodiment 17 | 2×102 | 5×102 |
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 acrylic fibres, are concretely comprised the following steps：
(1) by 200g graphenes and 2kg acrylic fibers section melt pelletization, obtain graphene and be combined acrylic fibers master batch；
(2) after the compound acrylic fibers master batch of above-mentioned graphene is mixed with the section of 13kg acrylic fibers, melt spinning obtains modified acrylic fibers
Fiber.
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 acrylic fibres, are modified by the way of normal temperature dipping, are 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) acrylic fiber is taken out afterwards in 25 DEG C of impregnated graphite alkene dispersion liquid 30min, dried, obtain modified acrylic fibers 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 acrylic fibres product, it is characterised in that inside the acrylic fiber of the modified acrylic fibres product and outer
There is graphene sheet layer in portion；
The acrylic fiber product includes acrylic fiber, Acrylic Fiber or acrylic fabric.
2. acrylic fiber product as claimed in claim 1, it is characterised in that be present in the stone outside the modified acrylic fibres
Black alkene lamella is more than the graphene sheet layer being present in inside modified acrylic fibres；
Preferably, the gross mass of graphene sheet layer is the 0.5 of acrylic fiber product gross mass in the modified acrylic fibres product
~3wt%；
Preferably, crystal region, noncrystalline domain and crystal region and the noncrystalline domain of fiber are included inside the modified acrylic fibres
Between gap；
Preferably, there is graphene sheet layer in the modified acrylic fibres internal junction crystalline region, while outside the modified acrylic fibres
There is graphene sheet layer；
Preferably, particle diameter≤20 μm of the graphene sheet layer；
Preferably, the particle diameter of the graphene sheet layer existed inside the modified acrylic fibres is less than 1 μm；
Preferably, the particle diameter of the graphene sheet layer existed outside the modified acrylic fibres is 1~20 μm.
3. modified fibre product as claimed in claim 1 or 2, it is characterised in that acrylic fibers in the modified acrylic fibres product
Ratio resistance≤1 × 10 of fiber5Ω·cm；
Preferably, after the modified acrylic fibres product is washed 50 times, ratio resistance≤1 × 10 of modified acrylic fibres5Ω·
cm。
4. the modified acrylic fibres product as described in one of claims 1 to 3, it is characterised in that the modified acrylic fibres system
Nano-cellulose is compounded with the acrylic fiber of product；
Preferably, the nano-cellulose is wrapped in the fiber internally and/or externally.
5. the preparation method of a kind of modified acrylic fibres product as described in one of Claims 1 to 4, it is characterised in that described
Method includes impregnating unmodified acrylic fiber product in graphene sheet layer dispersion liquid, afterwards through supercooling, drying, obtains
Modified acrylic fibres product after processing；
Wherein, the temperature of the dipping is more than glutinous stream temperature of the glass transition temperature less than acrylic fibers of acrylic fibers；
Preferably, the dipping temperature is 80~100 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 dispersion liquid be below 2wt%, preferably below 1wt%, 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 acrylic fiber product
Impregnate and be carried out in two steps in graphene sheet layer dispersion liquid, specifically include following steps：
(A1) by unmodified acrylic fiber article impregnation into the first graphene sheet layer dispersion liquid, the first dipping acrylic fiber 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 acrylic fiber article impregnation is obtained into the second dipping acrylic fibers 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 more than glutinous stream temperature of the glass transition temperature less than acrylic fibers of acrylic fibers,
Preferably 80~100 DEG C, and the step (A2) dipping temperature is less than step (A1) dipping temperature.
9. a kind of purposes of the modified acrylic fibres product as described in one of Claims 1 to 4, it is characterised in that the modified nitrile
Synthetic fibre fibre is used to prepare home textile, underwear, protective garment, thermal cloth, socks.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710443946.9A CN107245878A (en) | 2017-06-13 | 2017-06-13 | A kind of modified acrylic fibres product, preparation method and its usage |
| PCT/CN2018/079035 WO2018166477A1 (en) | 2017-03-15 | 2018-03-14 | Modified fibre product, preparation method therefor and use 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710443946.9A CN107245878A (en) | 2017-06-13 | 2017-06-13 | A kind of modified acrylic fibres product, preparation method and its usage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107245878A true CN107245878A (en) | 2017-10-13 |
Family
ID=60018181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710443946.9A Pending CN107245878A (en) | 2017-03-15 | 2017-06-13 | A kind of modified acrylic fibres product, preparation method and its usage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107245878A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486863A (en) * | 2018-04-24 | 2018-09-04 | 济南圣泉集团股份有限公司 | A kind of grapheme material modified fabric of antistatic and preparation method thereof |
| 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 |
| CN109943950A (en) * | 2019-04-02 | 2019-06-28 | 上海锦湾实业有限公司 | A kind of printing belt perspires the manufacturing method of acrylic fiber with warming moisture-absorbing |
| CN109972386A (en) * | 2017-12-27 | 2019-07-05 | 东丽先端材料研究开发（中国）有限公司 | A kind of conductive yarn and its product |
| CN110344164A (en) * | 2019-07-16 | 2019-10-18 | 无锡红豆纺织服装有限公司 | The method for weaving and underwear of the super warm soft highly-elastic type fever seamless fabric of suede |
| CN110711070A (en) * | 2019-09-25 | 2020-01-21 | 张小伏 | Preparation method of far infrared graphene condom |
Citations (4)
| 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 |
| CN106245441A (en) * | 2016-07-29 | 2016-12-21 | 佛山市高明区诚睿基科技有限公司 | A kind of Graphene modification composite glass fiber is in the application of glass fiber filter paper |
| CN106930097A (en) * | 2017-03-15 | 2017-07-07 | 山东圣泉新材料股份有限公司 | A kind of modified fibre product, preparation method and its usage |
-
2017
- 2017-06-13 CN CN201710443946.9A patent/CN107245878A/en active Pending
Patent Citations (4)
| 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 |
| CN106245441A (en) * | 2016-07-29 | 2016-12-21 | 佛山市高明区诚睿基科技有限公司 | A kind of Graphene modification composite glass fiber is in the application of glass fiber filter paper |
| CN106930097A (en) * | 2017-03-15 | 2017-07-07 | 山东圣泉新材料股份有限公司 | A kind of modified fibre product, preparation method and its usage |
Non-Patent Citations (1)
| Title |
|---|
| 上海纺织工学院: "《腈纶生产工艺及其原理》", 31 July 1976, 上海人民出版社 * |
Cited By (6)
| 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 |
| CN109972386A (en) * | 2017-12-27 | 2019-07-05 | 东丽先端材料研究开发（中国）有限公司 | A kind of conductive yarn and its product |
| CN108486863A (en) * | 2018-04-24 | 2018-09-04 | 济南圣泉集团股份有限公司 | A kind of grapheme material modified fabric of antistatic and preparation method thereof |
| CN109943950A (en) * | 2019-04-02 | 2019-06-28 | 上海锦湾实业有限公司 | A kind of printing belt perspires the manufacturing method of acrylic fiber with warming moisture-absorbing |
| CN110344164A (en) * | 2019-07-16 | 2019-10-18 | 无锡红豆纺织服装有限公司 | The method for weaving and underwear of the super warm soft highly-elastic type fever seamless fabric of suede |
| CN110711070A (en) * | 2019-09-25 | 2020-01-21 | 张小伏 | Preparation method of far infrared graphene condom |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107245878A (en) | A kind of modified acrylic fibres product, preparation method and its usage | |
| CN106930097A (en) | A kind of modified fibre product, preparation method and its usage | |
| CN107245879A (en) | A kind of modified polyester fibre product, preparation method and its usage | |
| CN106930096A (en) | A kind of modified fibre product, preparation method and its usage | |
| JP6852200B2 (en) | Modified textile products, preparation methods and their use | |
| CN106948171B (en) | Post-treatment method of fiber product, obtained modified fiber product and application thereof | |
| CN106930098A (en) | A kind of composite fibre, preparation method and its usage | |
| CN107829294A (en) | A kind of modified polyester fibre production method | |
| CN106930099A (en) | A kind of composite fibre, preparation method and its usage | |
| CN106996035A (en) | Fabric with conductive flame retardant coating and preparation method thereof | |
| CN106948170A (en) | A kind of post-processing approach of fibre, obtained modified fibre product and application thereof | |
| CN107254774A (en) | A kind of modified nylon fibre, preparation method and its usage | |
| CN110284322A (en) | Carbon-based fire-retardant compound fabric of a kind of compliant conductive fever and preparation method thereof | |
| CN112064168B (en) | Heating anti-pilling fabric | |
| CN106079761B (en) | A kind of nanofiber high magnification hydrophilic nonwoven material and preparation method | |
| CN107805938A (en) | A kind of modified polyester fibre | |
| CN108951122A (en) | A kind of production method of modified polyester fibre | |
| CN103653318A (en) | Woolen sweater and production method thereof | |
| JP5329468B2 (en) | Long and short composite yarn suitable for lightweight heat-insulated knitted fabric | |
| CN113981675B (en) | Preparation method of photo-induced heating textile | |
| CN109137478A (en) | A kind of production method of conductive dacron fibre | |
| CN109594325A (en) | A kind of nanometic zinc oxide rod array it is modified lead wet cotton fiber or its fabric and preparation method thereof | |
| CN108588942A (en) | A kind of acrylic fibers copper facing-boron alloy electrically conductive filament and preparation method thereof | |
| CN107956108A (en) | A kind of acrylic fibers electrically conductive filament and its preparation method for being complexed doping method | |
| CN108796645A (en) | Cool fiber and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171013 |
|
| RJ01 | Rejection of invention patent application after publication |