CN108018615A - A kind of preparation method of the polyacrylonitrile fibre of surface coating graphene oxide - Google Patents
A kind of preparation method of the polyacrylonitrile fibre of surface coating graphene oxide Download PDFInfo
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- CN108018615A CN108018615A CN201711434616.XA CN201711434616A CN108018615A CN 108018615 A CN108018615 A CN 108018615A CN 201711434616 A CN201711434616 A CN 201711434616A CN 108018615 A CN108018615 A CN 108018615A
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- polyacrylonitrile
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
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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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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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
- D06M2101/18—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
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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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Abstract
The present invention relates to a kind of preparation method of surface coating graphene oxide polyacrylonitrile fibre, mother liquor is coated by polyacrylonitrile, the compound alkalescence for preparing of graphene oxide, " being coated with base " is carried out to polyacrylonitrile matrix fiber, improves the caking property of " different base coating " during graphene oxide coating polyacrylonitrile matrix fiber.Meanwhile weak base aqueous mother liquor can carry out polyacrylonitrile fibre surface the etching of low degree, form coarse surface, further improve the cementability of fiber and mother liquor while not damaging substrate fibre strength.Invention not only improves polyacrylonitrile fibre and the problem of graphene oxide cementability, while impart the performances such as the excellent antistatic, sterilization of polypropylene fibre, uvioresistant.
Description
Technical field
The present invention relates to a kind of preparation of surface coating graphene oxide polyacrylonitrile fibre.
Technical background
Polyacrylonitrile fibre, refers to fine made of acrylonitrile content occupies the acrylic copolymer of more than 85wt%
Dimension.Polyacrylonitrile fibre is currently one of most important kind in civilian synthetic fibers, as important in China's textile industry
Part, polyacrylonitrile fibre have excellent flexibility, resilience and warmth retention property, referred to as synthetic wool, are weaving
Field is widely used.With the raising that people require textile, virgin pp nitrile fiber is difficult to meet people's
Demand, the multifunction of polyacrylonitrile fibre, i.e., antistatic, antibacterial, UV resistance, far infrared etc. are by widespread demand, pin of the present invention
To the deficiencies in the prior art, multifunction polyacrylonitrile fibre is prepared for by the coating of same base.The public affairs such as patent CN104163578A
The preparation method of cloth graphene oxide and graphene coating fiber, makes the antistatic property of fiber obtain very big change
It is kind, but graphene oxide is " different base coating " with graphene coating matrix fiber, caking property is not strong, easy to fall off, especially oxygen
Graphite alkene does not have the protection chance water of polymer soluble in water, causes the properties of coating fiber to be damaged.
The content of the invention
Technical problem：For in the prior art, the different base coating cementability of graphene oxide coating matrix fiber kind is poor and real
With the deficiency of the technical problems such as effect difference, there is provided a kind of high-adhesion, high stability, the graphene oxide-poly- third of multifunction
The preparation method of the compound mother liquor coating polypropylene fibre of alkene nitrile
Technical solution：A kind of preparation method of surface coating graphene oxide polyacrylonitrile fibre, includes the following steps：
(1) according to 20:Polyacrylonitrile powder is dissolved in solvent by 80 quality proportioning, is dispersed with stirring uniformly, is added a small amount of
Ammonium hydroxide, adjusts 7-8 by solution pH value, then adds spherical graphene oxide, the quality of the graphene oxide is polyacrylonitrile
The 0.5%-1% of powder；Stirring is uniformly dispersed and is fully deployed to spherical graphene oxide, obtains mother liquor.
(2) according to 98:2:Acrylonitrile, acrylic acid, solvent are uniformly mixed by 250 proportioning, obtain mixed liquor a；Take certain
The initiator A IBN of amount is added in solvent, obtains initiator solution, wherein, the quality of the initiator A IBN for acrylonitrile and
The 0.4% of acrylic acid gross mass；Initiator solution is added in the mixed liquor a that step 2 configures, it is 20% to obtain solid content
Mixed liquor b；It is transferred in reaction kettle, when reaction 10-24 is small at 60 DEG C, while is passed through nitrogen and makees protective gas.
(3) powder that step 2 is prepared is redissolved in solvent, prepares spinning solution.Utilize wet spinning technology system
Standby polyacrylonitrile fibre, after stretch processing, the mother liquor prepared by step (1) coated with base, surface painting is obtained after dry
Cover the polypropylene fibre of graphene oxide.
The beneficial effects of the present invention are：By the way that graphene oxide is dispersed in polyacrylonitrile solution, and by mother liquor tune
To alkalescence state, graphene oxide is fully unfolded in polyacrylonitrile solution, and be unlikely to form a large amount of folds and lead
Cause to reunite.Meanwhile weakly alkaline solution has certain corrasion to polyacrylonitrile matrix fiber, be conducive to mother liquor and be coated in fiber
Surface, polyacrylonitrile and graphene oxide in mother liquor etch to form physical crosslinking by the smile of groove and fiber surface,
It is bonding with matrix fiber to be conducive to mother liquor.Further, since polyacrylonitrile have in DMAc and DMF with graphene oxide it is excellent
Different dissolubility, the compound mother liquor coating polyacrylonitrile matrix fiber of preparation is to be coated with base, has excellent compatibility, mother liquor
It is preferable with the cementability of matrix fiber.Simultaneously as graphene oxide is surrounded by polymer, there is more excellent waterproof, moisture-proof
Function, can keep the functions such as antistatic, UV resistance, sterilization and far infrared long-term and stably.
Embodiment
Embodiment 1
(1) 200g polyacrylonitrile powders are weighed respectively to be dissolved in 800gDMAc, be dispersed with stirring uniformly, add a small amount of ammonium hydroxide,
Solution pH value is adjusted to 7-8, the spherical graphene oxide powders of 1g is then added, stirs at the same time, step up stir speed (S.S.), extremely
Spherical graphene oxide is uniformly dispersed and is fully deployed, and gives over to spare.
(2) acrylonitrile, acrylic acid, solvent for weighing 980g, 20g, 2500g respectively are added in polymeric kettle in batches, together
When stir mixing to uniform；
(3) weigh 4g initiator As IBN to be added in remaining 2500g, stirring is added to reaction to being completely dispersed uniformly
In kettle, 60 DEG C of controlling reaction temperature, when reaction 10 is small, while is passed through nitrogen and makees protective gas.
(4) after reaction, discharging, boiling, the powder of preparation is redissolved in solvent, prepare spinning solution.By
Filter, deaeration, are repeated several times, and adjust coagulating bath and spinning solution temperature.Polyacrylonitrile-oxidation stone is prepared using wet spinning technology
Black alkene fiber, then by stretch improve intensity, stretching approach include water-bath stretching, high steam stretching, high pressure dry heat drafting,
High pressure perseverance hot gas spring etc., then carries out the mother liquor prepared by step (1) to prepare surface coating oxygen with the process such as base coating, dry
Graphite alkene polypropylene fibre, labeled as PAN-GO-1.
Comparative example one
(1) 800gDMAc is weighed, adds a small amount of ammonium hydroxide, is dispersed with stirring uniformly, solution pH value is adjusted to alkalescence, then
The spherical graphene oxides of 1g are added, stirs at the same time, steps up stir speed (S.S.), are uniformly dispersed to spherical graphene oxide and complete
Expansion, gives over to spare.
(2) acrylonitrile, acrylic acid, solvent for weighing 980g, 20g, 2500g respectively are added in polymeric kettle in batches, together
When stir mixing to uniform；
(3) the initiator A IBN of 4g is taken to be added in the solvent of 2500g, stirring is added to reaction to being completely dispersed uniformly
In kettle, 60 DEG C of controlling reaction temperature, when reaction 10 is small, while is passed through nitrogen and makees protective gas.
(4) after reaction, discharging, boiling, the powder of preparation is redissolved in solvent, prepare spinning solution.By
Filter, deaeration, are repeated several times, and adjust coagulating bath and spinning solution temperature.Polyacrylonitrile-oxidation stone is prepared using wet spinning technology
Black alkene fiber, carries out the mother liquor prepared by step (1) with the process preparation such as base coating, dry surface coating oxidation stone after stretching
Black alkene polypropylene fibre, labeled as PAN-GO-2.
Comparative example two
(1) acrylonitrile, acrylic acid, solvent for weighing 980g, 20g, 2500g respectively are added in polymeric kettle in batches, together
When stir mixing to uniform；
(2) 4g initiator As IBN is weighed to add in 2500g solvents, stirring is added in reaction kettle to being completely dispersed uniformly,
60 DEG C of controlling reaction temperature, when reaction 10 is small, while is passed through nitrogen and makees protective gas.
(3) after reaction, discharging, boiling, the powder of preparation is redissolved in solvent, prepare spinning solution.By
Filter, deaeration, are repeated several times, and adjust coagulating bath and spinning solution temperature.Polyacrylonitrile-oxidation stone is prepared using wet spinning technology
Black alkene fiber, carries out the mother liquor prepared by step (1) with the process preparation such as base coating, dry surface coating oxidation stone after stretching
Black alkene polypropylene fibre, labeled as PAN-GO-0.
Spinning, coating parameters all same used by embodiment 1 and comparative example 1-2.By mechanical test, PAN-GO-
0th, the tensile strength of PAN-GO-1, PAN-GO-2 are respectively 44.23cN/dtex, 44.46cN/dtex, 48.23cN/dtex, weak
The compound mother liquor coating polyacrylonitrile fibre of alkalescence is not only without the intensity because of composite fibre prepared by etching reduction, on the contrary to poly-
Dralon plays humidification；PAN-GO-2, PAN-GO-1 are respectively provided with excellent antistatic property, bactericidal properties and remote
Infrared property, PAN-GO-0 do not possess these performances, are tested by environmental simulation, and the feature of PAN-GO-1 has preferably surely
Qualitative and durability, PAN-GO-2 do not possess persistence and weatherability, and graphene oxide is easily peeled off from polyacrylonitrile fibre.
Embodiment 2
(1) 200g polyacrylonitrile powders are weighed respectively to be dissolved in 800gDMF, be dispersed with stirring uniformly, add a small amount of ammonium hydroxide, will
Solution pH value is adjusted to alkalescence, is then added the spherical graphene oxide powders of 2g, is stirred at the same time, step up stir speed (S.S.),
It is uniformly dispersed and is fully deployed to spherical graphene oxide, gives over to spare.
(2) acrylonitrile, acrylic acid, solvent for weighing 980g, 20g, 2500g respectively are added in polymeric kettle in batches, together
When stir mixing to uniform；
(3) weigh 4g initiator As IBN to be added in 2500g solvents, stirring is added to reaction kettle to being completely dispersed uniformly
In, 60 DEG C of controlling reaction temperature, when reaction 24 is small, while is passed through nitrogen and makees protective gas.
(4) after reaction, discharging, boiling, the powder of preparation is redissolved in solvent, prepare spinning solution.By
Filter, deaeration, are repeated several times, and adjust coagulating bath and spinning solution temperature.Polyacrylonitrile-oxidation stone is prepared using wet spinning technology
Black alkene fiber, then by water-bath stretching, high steam stretching, high pressure dry heat drafting, high pressure perseverance hot gas spring, then by step
(1) mother liquor prepared by carries out preparing surface coating graphene oxide polypropylene fibre with the process such as base coating, dry.
By test, the tensile strength for coating fiber is 48.68cN/dtex, and sheet resistance is 6.5*10^5 Ω, is had excellent
Different antistatic property, while there is bactericidal property, UV resistance and far infrared performance.Tested by environmental simulation, fiber tool
There are excellent stability and durability.
Claims (2)
1. a kind of preparation method of the polyacrylonitrile fibre of surface coating graphene oxide, it is characterised in that comprise the following steps：
(1) according to 20:Polyacrylonitrile powder is dissolved in solvent by 80 quality proportioning, is dispersed with stirring uniformly, is added a small amount of ammonium hydroxide,
Solution pH value is adjusted into 7-8, then adds spherical graphene oxide, the quality of the graphene oxide is polyacrylonitrile powder
0.5%-1%；Stirring is uniformly dispersed and is fully deployed to spherical graphene oxide, obtains mother liquor.
(2) according to 98:2:Acrylonitrile, acrylic acid, solvent are uniformly mixed by 250 proportioning, obtain mixed liquor a；Take a certain amount of
Initiator A IBN is added in solvent, obtains initiator solution, wherein, the quality of the initiator A IBN is acrylonitrile and propylene
The 0.4% of sour gross mass；Initiator solution is added in the mixed liquor a that step 2 configures, obtains the mixing that solid content is 20%
Liquid b；It is transferred in reaction kettle, when reaction 10-24 is small at 60 DEG C, while is passed through nitrogen and makees protective gas.
(3) powder that step 2 is prepared is redissolved in solvent, prepares spinning solution.Prepared using wet spinning technology poly-
Dralon, after stretch processing, the mother liquor prepared by step (1) coat with base, coating oxygen in surface is obtained after dry
The polypropylene fibre of graphite alkene.
2. according to claim 1, it is characterised in that：The solvent can be DMAc, DMF, DMSo.
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| CN201711434616.XA CN108018615A (en) | 2017-12-26 | 2017-12-26 | A kind of preparation method of the polyacrylonitrile fibre of surface coating graphene oxide |
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| CN201711434616.XA CN108018615A (en) | 2017-12-26 | 2017-12-26 | A kind of preparation method of the polyacrylonitrile fibre of surface coating graphene oxide |
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| CN107059248A (en) * | 2017-03-29 | 2017-08-18 | 东华大学 | A kind of graphene oxide monolayer modifies the preparation method of polyacrylonitrile nanofiber film |
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| CN102704027A (en) * | 2012-06-14 | 2012-10-03 | 东华大学 | Preparation method for graphene oxide-modified PAN carbon fiber precursor |
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| CN104163578A (en) * | 2014-07-22 | 2014-11-26 | 杭州杭复新材料科技有限公司 | Preparation method of graphene coated composite glass fiber |
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