CN107938009B - Graphene oxide modified fiber and preparation method and application thereof - Google Patents
Graphene oxide modified fiber and preparation method and application thereof Download PDFInfo
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- CN107938009B CN107938009B CN201711244394.5A CN201711244394A CN107938009B CN 107938009 B CN107938009 B CN 107938009B CN 201711244394 A CN201711244394 A CN 201711244394A CN 107938009 B CN107938009 B CN 107938009B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002516 radical scavenger Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
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- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 239000003431 cross linking reagent Substances 0.000 claims description 52
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
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- 229920005989 resin Polymers 0.000 claims description 11
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- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
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- 150000002576 ketones Chemical class 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
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- 150000001336 alkenes Chemical class 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
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- 239000010703 silicon Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- TVFDJXOCXUVLDH-RNFDNDRNSA-N cesium-137 Chemical compound [137Cs] TVFDJXOCXUVLDH-RNFDNDRNSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-IGMARMGPSA-N iridium-192 Chemical compound [192Ir] GKOZUEZYRPOHIO-IGMARMGPSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a graphene oxide modified fiber and a preparation method and application thereof. A preparation method of graphene oxide modified fibers comprises the following steps: mixing graphene oxide, a free radical scavenger, water and a monomer of a fiber-forming polymer to prepare a mixed solution; irradiating the mixed solution in an inert atmosphere to obtain a spinning solution; and spinning the spinning solution to obtain the graphene oxide modified fiber. The invention solves the problem of low conductivity of the graphene oxide modified fiber and the product thereof, the graphene oxide modified fiber prepared by the method has the advantages of high conductivity, light weight, static resistance, wide application range and the like, and the preparation method does not need to introduce a reducing agent and an initiator, thereby reducing the pollution to the environment.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a graphene oxide modified fiber and a preparation method and application thereof.
Background
The conductive fiber has good conductivity and durability, particularly has good durable antistatic property under low humidity, and has good electromagnetic shielding function when the conductive layer reaches a certain thickness or the conductive components reach a certain proportion, so the conductive fiber has great application in the fields of industry, civil use and the like, such as conductive nets and conductive work clothes in the electronics and power industry, electric heating clothes and electric heating bandages in the medical industry, electromagnetic shielding covers in the aviation, aerospace and precision electronics industries and the like. The antistatic mechanism of the conductive fibers is to generate corona discharge between the conductive fibers. The corona discharge is a very gentle discharge form, and when the static voltage reaches a certain value, the corona discharge without sparks is generated to eliminate the static electricity. This phenomenon is generally known as the phenomenon in which conductive fibers in a fabric, under the action of an electrostatic field, ionize the surrounding air to form positive and negative ions, one of which neutralizes the static charge of the fabric in a manner opposite to that of the fabric, and the other of which neutralizes the environment or the ground, thereby eliminating the static electricity.
At present, the conductive fibers generally have the problems of higher processing cost, more complex process and the like, which limits the production of the conductive fibers to a certain extent and the use and popularization, so that the conductive fibers are mainly applied to the high-tech field at present and have fewer varieties for civil use. With the improvement of living standard of people and the enhancement of self health protection consciousness, the popularization and the use of the civil conductive fiber inevitably become a trend, so the processing of the conductive fiber should be developed towards the direction of simple process and low cost, and the endowment of the conductivity of the common fiber is one of the ways for solving the problems.
Graphene is a polymer formed from carbon atoms as SP2The layered structure which is formed by the compact arrangement of the hybrid mode and is similar to a honeycomb structure is widely concerned by people because of excellent heat conduction and electric conduction performance, and is considered to be one of the choices of the electric conduction performance of the modified fiber. However, since the surface of graphene is in an inert state, the interaction with other media is weak, and strong van der waals force exists between graphene sheets, the graphene sheets are easy to agglomerate, and are difficult to be uniformly dispersed in the fiber or on the surface, and the excellent performance of graphene cannot be fully retained in the composite material. Graphene oxide is a product of chemically oxidizing and stripping graphite powder, is a single atomic layer, can be expanded to tens of micrometers in the transverse dimension at any time, has excellent dispersibility in water, and can be uniformly dispersed in fibers instead of graphene, but the requirement of a conductive material cannot be met by directly adding graphene oxide to the fibers because the conductivity of graphene oxide is poorer than that of common graphite.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention mainly aims to provide a preparation method of graphene oxide modified fibers, which solves the problem of low conductivity of the graphene oxide modified fibers and products thereof, and the graphene oxide modified fibers prepared by the method have the advantages of high conductivity, light weight, static resistance, wide application range and the like.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of graphene oxide modified fibers comprises the following steps:
mixing graphene oxide, a free radical scavenger, water and a monomer of a fiber-forming polymer to prepare a mixed solution;
irradiating the mixed solution in an inert atmosphere to obtain a spinning solution;
and spinning the spinning solution to obtain the graphene oxide modified fiber.
According to the preparation method, the graphene oxide and the fiber-forming polymer are bonded together mainly through three procedures of mixing, irradiation and spinning, and the graphene oxide is reduced through irradiation, namely, a layer of reduced graphene oxide is continuously coated inside the fiber, so that the conductivity of the fiber is endowed.
However, the modification of the fiber surface of the present invention is different from the physical coating in the prior art, and the following difficulties need to be overcome in the process of the present invention:
firstly, the problem of poor conductivity of graphene oxide is solved: the invention solves the problem by double treatment of a free radical scavenger and irradiation, wherein the irradiation can ionize water to generate H & free radical and hydrated electron e- aqAnd OH & free radical, wherein the H & free radical and hydrated electron have strong reduction effect, the H & free radical and hydrated electron are utilized to reduce the graphene oxide into graphene, and the OH & free radical is removed by utilizing the free radical scavenger.
And secondly, the continuous distribution of the graphene oxide in the fiber must be ensured, so that current continuously passes through, and the electric conduction is really realized. In this regard, the invention enables the surface of the graphene oxide to generate a plurality of free radicals through irradiation, and the plurality of free radicals increase the cross-linking points between the graphene oxide and the fiber-forming polymer and monomers thereof, so that the graphene oxide is continuously and uniformly bonded on the molecular layer of the fiber-forming polymer, that is, the graphene oxide is continuously distributed in the fiber.
And thirdly, the graphene oxide is added in the monomer polymerization process, so that the graphene oxide can be crosslinked or coated in multiple dimensions such as molecules and intermolecular, and the comprehensive performance of the fiber is improved on the organic whole.
In addition, the irradiation provides heat for the polymerization reaction and the crosslinking reaction, and promotes the crosslinking reaction between the graphene oxide and the polymer and the rapid polymerization reaction between monomers.
The method is different from the method of introducing the graphene material before the existing spinning, and the polymerization process and the graphene oxide crosslinking process are simultaneously completed, namely, the polymerization reaction of the monomer, the crosslinking of the monomer and the graphene oxide and the crosslinking of the polymer and the graphene oxide are simultaneously carried out under irradiation. The invention adopts the above process to achieve the following purposes: firstly, two-step reaction is combined into one step, so that the time is saved, and the production efficiency is improved; and secondly, the graphene oxide modifies the fibers in multiple dimensions, including cross-linking on monomers, cross-linking on oligomers, cross-linking on high polymers and the like.
The raw material-graphene oxide used in the invention generally refers to graphene oxide prepared by any method (the name definition is shown in graphene alliance standard T/CGIA 001-2017).
The fiber-forming polymer is a synthetic high molecular polymer capable of being made into fibers, not only has the capability of forming fibers, but also must be completely dissolved in a proper solvent to form a viscous concentrated solution; or melt-converted into a viscous state at an elevated temperature without decomposition to facilitate solution spinning or melt spinning. For example, polypropylene, polyacrylonitrile, polyamide, polyvinyl formal, polyethylene terephthalate, polyurethane, polyvinyl chloride, polycarbonate, etc., and the fibers made of polypropylene, acrylic, vinylon, spandex, polyester, polyvinyl chloride, etc.
The monomers of the present invention may be liquid or solid. The liquid monomer is a monomer which is liquid at normal temperature and can be directly polymerized under irradiation. The solid monomers form a flowing liquid after being dissolved in the corresponding solvent, and can also be polymerized under irradiation. That is, when the monomer is a solid monomer insoluble in water, a solvent is further added to the mixed solution to dissolve the monomer.
The above preparation method of the present invention can be further improved, for example:
preferably, the concentration of graphene oxide in the mixed solution is 30mg/mL or less, preferably 20mg/mL or less, and more preferably 10-20 mg/mL.
The concentration of graphene oxide can be any value of 30mg/mL or less, for example, 30mg/mL, 29mg/mL, 28mg/mL, 27mg/mL, 26mg/mL, 25mg/mL, 24mg/mL, 23mg/mL, 20mg/mL, 18mg/mL, 15mg/mL, 10mg/mL, 8mg/mL, 5mg/mL, 1mg/mL, 0.5mg/mL, 0.1mg/mL, etc., with preferred ranges of 20mg/mL or less, more preferably 10-20mg/mL or 15-20mg/mL, etc.
Preferably, the weight content of the water in the mixed solution is 30-100 mg/mL, such as 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL, 100 mg/mL.
Preferably, the concentration of the radical scavenger in the mixed solution is 5 to 50 mg/mL.
Preferably, the radical scavenger is one or more of an alcohol, an amine and a ketone, such as an alcohol, an amine, a ketone, a mixture of an alcohol and an amine, a mixture of an alcohol and a ketone, or a mixture of an amine and a ketone, or a mixture of an alcohol, an amine and a ketone.
Wherein, the alcohol is preferably selected from one or more of methanol, ethanol and isopropanol; such as methanol, ethanol, isopropanol, a mixture of methanol and ethanol, a mixture of methanol and isopropanol, a mixture of ethanol and isopropanol, or a mixture of methanol, ethanol and isopropanol.
The amine is preferably selected from one or more of ethanolamine, diethanolamine and triethanolamine, for example ethanolamine, diethanolamine, triethanolamine, a mixture of ethanolamine and diethanolamine, a mixture of ethanolamine and triethanolamine, a mixture of ethanolamine, diethanolamine and triethanolamine; among the above schemes, triethanolamine is preferred.
The ketone is acetone or butanone or a mixture of the acetone and the butanone.
Preferably, the weight ratio of the monomers of the fiber-forming polymer to the graphene oxide is 90-100: 3-10.
Before spinning, the more graphene oxide is not added into the monomer mixed solution, the better the conductivity is, and through examination, it is found that when the weight ratio of the monomer of the fiber-forming polymer to the graphene oxide is 90-100:3-10, better synergistic effects can be obtained, such as 90:3, 100:3, 90:5, 95:3, 97:3, 90:5, 100:4, 100:6, 100:8, 100:9, 100:10, 90:10, and the like.
Preferably, the weight ratio of the radical scavenger to the graphene oxide is 0.1-3: 3, more preferably 0.1-2: 3, 0.5-2: 3, 1-2: 3, 1.5-2: 3, and the like.
Preferably, the weight ratio of water to graphene oxide is 5-10:3, more preferably 5-8:3, 5-7:3, 5-6:3, and the like.
Preferably, the dose rates of the irradiation are: 1-500 KGy/h.
The irradiation dose has an important influence on the connection strength between the graphene oxide and the cellulose, and through screening, the more suitable irradiation dose is 1-500KGy/h, more preferably 100-200KGy/h, such as 1KGy/h, 10KGy/h, 20KGy/h, 50KGy/h, 100KGy/h, 150KGy/h, 200KGy/h, 250KGy/h, 300KGy/h, 350KGy/h, 400KGy/h, 450KGy/h or 500 KGy/h. In actual practice, a constant irradiation dose may not be achieved, allowing for a range of fluctuations.
The radiation source for irradiation is not limited in general, and is, for example, commonly used-60: (60Co) gamma-ray radiation source or electron accelerator, or α radioactive source of cesium-137, iridium-192, gamma-ray source, etc., preferably-60: (60Co) gamma radiation source or electron accelerator.
The means of spinning in the present invention is not particularly limited, and for example, the spinning is electrostatic spinning or solution spinning, and the spinning solution can be adjusted suitably according to the spinning process.
Preferably, a cross-linking agent is also added when the mixed solution is prepared; the crosslinking agent may increase the amount of crosslinking between the graphene oxide and the fiber-forming polymer and the stability of the crosslinking.
The cross-linking agent is one or more of an alkene cross-linking agent, an organic silicon cross-linking agent and an epichlorohydrin resin cross-linking agent.
The cross-linking agent is used as a bridge between the graphene oxide and the fiber-forming polymer, and is inserted into a lamellar structure of the graphene oxide on one hand, so that the graphene oxide is inserted into the molecules of the fiber-forming polymer and can keep excellent characteristics, and on the other hand, the graphene oxide and the fiber-forming polymer are cross-linked into a net structure, so that the excellent characteristics of the fiber-forming polymer are kept, and the bonding strength between the graphene oxide and the fiber-forming polymer is improved. Based on the above purposes, one or more of an alkene cross-linking agent, an organic silicon cross-linking agent and an epichlorohydrin resin cross-linking agent are preferred, and all the cross-linking agents can achieve the above purposes and obtain better effects. These crosslinking agents may be used alone or in any combination thereof, and for example, when an olefinic crosslinking agent is used in combination with a silicone crosslinking agent, or a silicone crosslinking agent is used in combination with an epichlorohydrin resin crosslinking agent, or a olefinic crosslinking agent is used in combination with an epichlorohydrin resin crosslinking agent, or a combination of an olefinic crosslinking agent, a silicone crosslinking agent and an epichlorohydrin resin crosslinking agent, a combination of the olefinic crosslinking agent, the silicone crosslinking agent and the epichlorohydrin resin crosslinking agent can provide a preferable overall effect.
Preferably, the alkene crosslinking agent is selected from one or more of polyethylene glycol diacrylate, polyethylene polyamine, melamine triallyl ester, triallyl cyanurate, trimethylolpropane tri- (3-ethyleneimino) -propionate.
Polyethylene glycol diacrylate, polyethylene polyamine, melamine triallyl ester, triallyl cyanurate and trimethylolpropane tri- (3-ethyleneimino) -propionate have stronger conjugation effect, and the formed crosslinking system is more stable.
Preferably, the silicone-based crosslinking agent is a silane coupling agent.
The silane coupling agent can not only enhance the stability of the combination of the fiber-forming polymer and the graphene oxideAnd the conductivity and aging resistance of the fiber can be improved. In principle, any silane coupling agent YSiX3All the n is 0-3; x is a hydrolyzable group, usually a chloro group, a methoxy group, an ethoxy group, a methoxyethoxy group, an acetoxy group, etc., which upon hydrolysis produces a silanol (Si (OH)3) And combines with inorganic substances to form siloxane; y is an organic functional group capable of reacting with the resin and is a vinyl group, an amino group, an epoxy group, a methacryloxy group, a mercapto group or a ureido group. Among the above types, vinyl silane, amino silane, epoxy silane, mercapto silane, methacryloxy silane, and the like can be used, and these crosslinking agents can be used alone or in combination, of which vinyl group is preferable.
Preferably, the epichlorohydrin resin crosslinking agent is a crosslinking agent DE, a crosslinking agent EH, a crosslinking agent FH or the like.
The epichlorohydrin resin crosslinking agent has the advantages of good solubility and mild use condition, DE, EH and FH can be used independently or in combination, and the crosslinking agent DE is preferably used independently.
Preferably, the weight ratio of the cross-linking agent to the graphene oxide in the mixed solution is 1-3: 1.
The weight ratio of the cross-linking agent to the graphene oxide may be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, and the like.
The graphene oxide modified fiber prepared by the preparation method provided by the invention is wide in application, and can be used for manufacturing conductive devices in multiple industries such as the electronic industry, the electric power industry, the aerospace industry and the like, wherein the conductive devices comprise electric heating fabrics, electromagnetic shielding fabrics or circuit boards, and specifically comprise conductive nets, conductive working clothes, electric heating bandages, electromagnetic shielding covers, circuit printing boards and the like.
In summary, compared with the prior art, the invention achieves the following technical effects:
(1) the graphene oxide is crosslinked inside the fiber in an irradiation mode, and the graphene oxide is reduced, so that the conductivity of the fiber is increased, the conductivity level at least equal to that of the traditional conductive fiber can be achieved, a better substitute is provided for the traditional conductive fiber, and the problems of complex process, high cost and the like of the traditional conductive fiber are solved.
(2) The stability of the graphene oxide modified fiber is improved by adding the cross-linking agent;
(3) according to the invention, graphene oxide is added into a fiber-forming polymer before spinning and polymerization, so that the comprehensive performance of the fiber is improved in multiple dimensions from the inside to the outside of a molecule and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphene oxide materials provided by the following embodiments of the present invention are of the types:
graphene oxide A: graphene oxide prepared by Hummers method.
And (3) graphene oxide B: graphene oxide prepared by the Brodie method.
Example 1
Preparation of modified Polyacrylonitrile fibers
(1): preparing mixed liquor containing graphene oxide A, wherein the mixed liquor comprises acrylonitrile, a free radical scavenger (isopropanol), graphene oxide A and deionized water, taking the raw materials, uniformly stirring, and obtaining mixed liquor with the following concentration, wherein the weight ratio of the acrylonitrile to the graphene oxide A is 90: 3:
the concentration of the free radical scavenger is 10mg/mL,
the concentration of the graphene oxide A is 30mg/mL,
the concentration of water was 30 mg/mL.
(2): and (3) placing the mixed solution in a closed container, removing air, introducing inert gas, and irradiating the mixed solution by using an electron accelerator.
The irradiation dose rate is 100KGy/h, and the irradiation time is 1 h.
(3): and (4) taking the solution after irradiation as spinning solution, and performing electrostatic spinning to obtain the polyacrylonitrile fiber.
And (5) carrying out performance test on the irradiated polyacrylonitrile fiber.
Examples 2 to 6
Examples 2 to 6 differ from example 1 only in the irradiation dose rates, the remaining steps and parameters being the same, the irradiation dose rates of examples 2 to 6 being: 1KGy/h, 10KGy/h, 50KGy/h, 200KGy/h, 500 KGy/h.
Examples 7 to 8
Examples 7 to 8 differ from example 1 only in the type of monomers and the remaining steps and parameters are the same, and the types of fibers of examples 7 to 8 are: propylene (example 7), toluene diisocyanate and ethylene glycol in a 3:2 molar ratio were mixed (example 8).
Examples 9 to 12
Examples 9 to 12 differ from example 1 only in the weight ratio of the polymer monomer to the graphene oxide, but the ratio of the graphene oxide to the radical scavenger and water was not changed, and the weight ratios of the polymer monomer to the graphene oxide were 95:3 (example 9), 100:3 (example 10), 10:1 (example 11), and 9:1 (example 12), respectively.
Examples 13 and 14
Examples 13 and 14 differ from example 1 only in the concentration of graphene oxide a in the mixed solution, which is: 20mg/mL and 10mg/mL, and under the condition that the proportion of the graphene oxide A, the free radical scavenger and the water is inconvenient, the concentration of other raw materials is changed correspondingly.
Examples 15 and 16
Examples 15 and 16 differ from example 1 in the type of radical scavenger, and the isopropyl alcohol of example 1 was replaced with: triethanolamine (example 15), acetone (example 16).
Example 17
Example 17 differs from example 1 in the type of graphene oxide, and graphene oxide a is replaced with graphene oxide B.
Examples 18 to 20
Examples 18 to 20 differ from example 1 only in that in step (1) a crosslinking agent is also added, the crosslinking agent being: polyethylene glycol diacrylate (example 18), a crosslinking agent DE (example 19), a crosslinking agent DE and a silane coupling agent monomer, etc. were recombined (example 20), and the concentrations of the crosslinking agents in the mixed solutions of examples 18 to 20 were all 30 mg/mL.
Example 21
Example 21 differs from example 18 only in the concentration of the crosslinking agent in the mixed solution: 90 mg/mL.
Example 22
Example 22 differs from example 1 in the ratio of the radical scavenger, water and graphene oxide a, and in the mixing prepared in the first step, the concentration of the radical scavenger is 30mg/mL, the concentration of the graphene oxide a is 30mg/mL, and the concentration of water is 50 mg/mL.
Example 23
Example 23 differs from example 1 in the ratio of the radical scavenger, water and graphene oxide a, and in the mixing prepared in the first step, the concentration of the radical scavenger is 1mg/mL, the concentration of the graphene oxide a is 30mg/mL, and the concentration of water is 100 mg/mL.
Comparative example 1
Comparative example 1 differs from example 1 in that no water was added to the mixture in the first step and the remaining steps and parameters were the same.
Comparative example 2
The difference between the comparative example 1 and the example 1 is that the radical scavenger is not added to the mixture in the first step, and the rest of the steps and parameters are the same.
Comparative example 3
The difference from example 1 is that the polymerization has been completed before irradiation, as follows:
(1): preparing mixed liquor containing graphene oxide A, wherein the mixed liquor comprises polyacrylonitrile, a free radical trapping agent (isopropanol), graphene oxide A, deionized water and dimethylformamide, uniformly stirring the above raw materials in the dimethylformamide, and obtaining mixed liquor with the following concentration, wherein the weight ratio of the polyacrylonitrile to the graphene oxide A is 90: 3:
the concentration of the free radical scavenger is 10mg/mL,
the concentration of the graphene oxide A is 30mg/mL,
the concentration of water was 30 mg/mL.
(2): and (3) placing the mixed solution in a closed container, removing air, introducing inert gas, and irradiating the mixed solution by using an electron accelerator.
The irradiation dose rate is 100KGy/h, and the irradiation time is 1 h.
(3): and (4) taking the solution after irradiation as spinning solution, and performing electrostatic spinning to obtain the polyacrylonitrile fiber.
And (5) carrying out performance test on the irradiated polyacrylonitrile fiber.
The properties of the fibers obtained in all the above examples and comparative examples are shown in Table 1.
TABLE 1 Properties of graphene oxide-modified fibers
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (15)
1. A preparation method of graphene oxide modified fibers is characterized by comprising the following steps:
mixing graphene oxide, a free radical scavenger, water and a monomer of a fiber-forming polymer to prepare a mixed solution;
irradiating the mixed solution in an inert atmosphere to obtain a spinning solution;
spinning the spinning solution to obtain graphene oxide modified fibers;
the fiber-forming polymer is polypropylene, polyacrylonitrile, polyamide, polyvinyl formal, polyurethane, polyethylene terephthalate, polyvinyl chloride or polycarbonate;
the concentration of the graphene oxide in the mixed solution is 10-20 mg/mL;
the irradiation dose rate is 1-500 KGy/h.
2. The method according to claim 1, wherein when the monomer is a solid monomer insoluble in water, a solvent is further added to the mixed solution to dissolve the monomer.
3. The method according to claim 1 or 2, wherein the radical scavenger is one or more of an alcohol, an amine and a ketone.
4. The method according to claim 3, wherein the alcohol is one or more selected from methanol, ethanol, and isopropanol.
5. The method according to claim 3, wherein the amine is one or more selected from the group consisting of ethanolamine, diethanolamine, and triethanolamine; the ketone is acetone or butanone or a mixture of the acetone and the butanone.
6. The method according to claim 5, wherein the amine is triethanolamine.
7. The preparation method according to claim 1, wherein the weight ratio of the monomers of the fiber-forming polymer to the graphene oxide is 90-100: 3-10.
8. The method according to claim 1, wherein the weight ratio of the radical scavenger to the graphene oxide is 0.1-3: 3.
9. The preparation method according to claim 1, wherein the weight ratio of the water to the graphene oxide is 5-10: 3.
10. The method of claim 1, wherein the spinning is electrospinning or solution spinning.
11. The method according to claim 1, wherein a crosslinking agent is further added when the mixed solution is prepared;
the cross-linking agent is one or more of an alkene cross-linking agent, an organic silicon cross-linking agent and an epichlorohydrin resin cross-linking agent.
12. The preparation method according to claim 11, wherein the alkene-based cross-linking agent is selected from one or more of polyethylene glycol diacrylate, polyethylene polyamine, melamine triallyl ester, triallyl cyanurate, trimethylolpropane tri- (3-ethyleneimino) -propionate;
the organic silicon cross-linking agent is a silane coupling agent;
the epichlorohydrin resin crosslinking agent is a crosslinking agent DE;
the weight ratio of the cross-linking agent to the graphene oxide in the mixed solution is 1-3: 1.
13. A graphene oxide-modified fiber obtained by the production method according to any one of claims 1 to 12.
14. The use of the graphene oxide-modified fiber of claim 13, wherein the graphene oxide-modified fiber is used for manufacturing conductive devices in the electronic industry, the electric power industry and the aerospace industry.
15. Use according to claim 14, wherein the electrically conductive means is an electro-thermal fabric, an electro-magnetic shielding fabric or a circuit board.
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| CN109082727A (en) * | 2018-07-12 | 2018-12-25 | 山东佳星环保科技有限公司 | A kind of preparation method for the polyester blended fabric that graphene is modified |
| CN108824760B (en) * | 2018-08-01 | 2019-06-04 | 上海天行新型材料有限公司 | A kind of foamed cement composite floor board and preparation method thereof of modified fibre enhancing |
| CN112090169A (en) * | 2020-08-12 | 2020-12-18 | 柳州紫荆技术转移中心有限公司 | Preparation method of graphene composite filtering material for efficient integrated water purification equipment for sewage treatment |
| CN113151911B (en) * | 2021-04-20 | 2022-11-04 | 东华大学 | A kind of preparation method of antistatic wool fabric |
| CN117568984B (en) * | 2023-11-28 | 2025-12-02 | 河北凤展织带有限公司 | A flexible heat-generating safety protective webbing and its manufacturing process |
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