CN115011070A - Electromagnetic shielding optical cable and preparation method thereof - Google Patents
Electromagnetic shielding optical cable and preparation method thereof Download PDFInfo
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- CN115011070A CN115011070A CN202210647533.3A CN202210647533A CN115011070A CN 115011070 A CN115011070 A CN 115011070A CN 202210647533 A CN202210647533 A CN 202210647533A CN 115011070 A CN115011070 A CN 115011070A
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- optical cable
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- carbon fiber
- melamine
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- 230000003287 optical effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 73
- 239000004917 carbon fiber Substances 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006260 foam Substances 0.000 claims abstract description 46
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000004964 aerogel Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000004005 microsphere Substances 0.000 claims description 26
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 26
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 25
- 229940078494 nickel acetate Drugs 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000013307 optical fiber Substances 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 10
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical compound C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 7
- 235000013922 glutamic acid Nutrition 0.000 claims description 7
- 239000004220 glutamic acid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- -1 dimethyl diamide Chemical compound 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002166 wet spinning Methods 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 239000002120 nanofilm Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4401—Optical cables
- G02B6/4429—Means specially adapted for strengthening or protecting the cables
- G02B6/443—Protective covering
-
- 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
- D06M2101/40—Fibres of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention discloses an electromagnetic shielding optical cable and a preparation method thereof, and relates to the technical field of communication optical cables. The electromagnetic shielding optical cable prepared by the invention comprises a sheath layer, a shielding layer and a cable core from outside to inside; the sheath layer is made of epoxy resin added with modified graphite aerogel; the shielding layer comprises a melamine foam layer, a foam metal layer and carbon fibers; modified graphite aerogel has improved the mechanical strength of restrictive coating, still possesses electromagnetic shielding performance, can react with the melamine foam blanket, with restrictive coating and shielding layer zonulae occludens, reinforcing optical cable intensity, at carbon fiber surface deposit foam metal, the shielding layer that the etherified melamine resin of cladding foaming made again for the electromagnetic wave can take place to reflect in the inside hole of shielding layer, the electromagnetic shielding nature of reinforcing optical cable.
Description
Technical Field
The invention relates to the technical field of communication optical cables, in particular to an electromagnetic shielding optical cable and a preparation method thereof.
Background
Fiber optic cables are manufactured to meet optical, mechanical, or environmental performance specifications and utilize one or more optical fibers disposed in a covering jacket as the transmission medium and may be used individually or in groups as telecommunication cable assemblies. The optical cable is mainly composed of optical fiber, plastic protective sleeve and plastic outer skin. The method is not only widely applied to the conventional communication field, but also applied to other high-tech fields such as sensing, measurement, control, data acquisition and the like, such as mining industry, aerospace industry, military, petroleum and natural gas, high-temperature medical application and the like. These fields may relate to specific application environments, such as high temperature environments, electromagnetic environments, etc.
However, most of the current researches on optical cables focus on the research on heat resistance and flame retardance, and little attention is paid to the optical cable applied to the field of electromagnetic shielding, so that the optical cable with good heat resistance, high strength and high electromagnetic shielding performance is researched and prepared by the application.
Disclosure of Invention
The invention aims to provide an electromagnetic shielding optical cable and a preparation method thereof, and aims to solve the problems in the background technology.
An electromagnetic shielding optical cable comprises a sheath layer, a shielding layer and a cable core from outside to inside, and is characterized in that the sheath layer is modified graphite aerogel; the cable core is an optical fiber.
Preferably, the modified graphite aerogel is prepared by introducing pyrrolidone microspheres between graphene layers; the pyrrolidone microspheres are prepared by reacting maleic anhydride, N-vinyl pyrrolidone and vinyl cyclohexyl ether.
Preferably, the shielding layer comprises a melamine foam layer, a foam metal layer and carbon fibers.
Preferably, the carbon fiber is prepared by performing preoxidation and carbonization on polyacrylonitrile after wet spinning; the foam metal layer is prepared by carrying out in-situ reduction on the carbon fiber by nickel sulfate, hydrazine hydrate and hexadecyl trimethyl ammonium bromide; the melamine foam layer is prepared by coating hexafluorobutanol etherified melamine formaldehyde resin outside a foam metal layer and foaming.
Preferably, the preparation method of the electromagnetic shielding optical cable comprises the following specific steps:
(1) dispersing graphene oxide in deionized water with the mass of 30-50 times that of the graphene oxide, ultrasonically dispersing for 20-30 min at 100-150 kHz, adding pyrrolidone microspheres with the mass of 0.25-0.35 time that of the graphene oxide, continuously ultrasonically dispersing for 20-30 min, transferring to a hydrothermal reaction kettle, reacting for 12-16 h at 180-200 ℃, freeze-drying in a freeze dryer at-50-60 ℃, and finally performing heat treatment for 2-3 h at 800-900 ℃ to obtain modified graphite aerogel;
(2) dispersing nickel acetate in deionized water with the mass 30-40 times that of the nickel acetate, uniformly stirring, adding 80-85% hydrazine hydrate with the mass fraction 3-5 times that of the nickel acetate, and stirring at 30-50 rpm for 0.5-1 h to prepare a nickel acetate solution; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 60-70%, heating to 80-90 ℃, reacting for 1-2 h, fishing out, washing with deionized water for 3-5 min, wiping dry, stretching to the diameter of 0.06-0.08 mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 3-5% which is 5-10 times that of the carbon fiber precursors, heating to 160-180 ℃, reacting for 0.5-1 h, adding a nickel acetate solution with the mass of 20-25 times that of the carbon fiber precursors and hexadecyl trimethyl ammonium bromide with the mass of 0.15-0.25 time that of the carbon fiber precursors, continuing to react for 6-8 h, transferring to a carbonization furnace, carbonizing at 500-1000 ℃ for 3-5 h under the nitrogen atmosphere, and preparing carbon fibers with foam metal layers;
(3) soaking carbon fibers with a foam metal layer in etherified melamine, adding sodium dodecyl benzene sulfonate which is 0.01-0.04 times of the mass of the etherified melamine, stirring at 2000-2500 rpm for 2-5 min, adding a foaming agent n-pentane which is 0.02-0.04 times of the mass of the etherified melamine and a catalyst oxalic acid which is 0.08-0.1 times of the mass of the etherified melamine, continuously stirring for 5-8 s, taking out the carbon fibers with the foam metal layer, coating a cable core, placing the cable core in a mold which is preheated at 90-100 ℃ for 3-5 min, sealing, placing the mold in a carbon fiber oven with the foam metal layer for foaming and curing, taking out the cable core after 2-3 h, and finally drying the cable core in a drying box for 24-48 h to obtain the cable core with the shielding layer;
(4) mixing the modified graphite aerogel, polyamide and epoxy resin according to a mass ratio of 2:0.5: 6-3: 0.8:8, putting the mixture into a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying box, and drying the mixture at the temperature of 60-80 ℃ for 5-6 hours to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 315-355 ℃, and the thickness of a sheath layer is 0.05-0.15 mm.
Preferably, in the step (1): the preparation method of the pyrrolidone microspheres comprises the following steps: mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 2:0.15: 10-4: 0.2:15, sequentially adding N-vinyl pyrrolidone of which the mass is 0.8-1.2 times that of the maleic anhydride, vinyl cyclohexyl ether of which the mass is 0.5-0.8 times that of the maleic anhydride and cross-linking agent divinylbenzene of which the mass is 0.02-0.05 times that of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 60-62 ℃ under the nitrogen atmosphere, reacting for 6-8 hours, ultrasonically dispersing for 2-3 minutes under 100-200 kHz, performing Soxhlet purification for 36-48 hours by using acetone, and finally drying in a vacuum drying oven at 45-55 ℃ to obtain the pyrrolidone microspheres.
Preferably, in the step (2): the preparation method of the carbon fiber precursor comprises the following steps: mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 1: 10-3: 10, heating to 85-100 ℃, mixing for 0.5-1 h under the assistance of 200-300W microwaves, adding glycerol 0.1-0.2 time of the mass of the polyacrylonitrile and thiourea 0.05-0.15 time of the mass of the polyacrylonitrile, uniformly mixing to prepare a spinning solution, and performing wet electrostatic spinning at 70-90 ℃ with a solidification temperature of 5-15 ℃ to prepare the carbon fiber precursor.
Preferably, in the step (3): the preparation method of the etherified melamine comprises the following steps: mixing melamine, paraformaldehyde and triethylamine according to the mass ratio of 1:6: 20-1: 8:40, heating to 90-95 ℃, continuously preserving heat for 1-2 hours after complete dissolution, adding hexafluorobutanol with the mass of 0.15-0.3 times of that of the melamine, adjusting the pH value to 5.2-5.5 with nitric acid, keeping the temperature at 90-95 ℃, reacting for 12-24 hours, and adjusting the pH value to 8-9 with triethylamine to obtain the etherified melamine.
Preferably, in the step (3): the cable core is an optical fiber with the diameter of 0.2-0.5 mm.
Preferably, in the step (4): the thickness of the shielding layer is 0.1-0.2 mm.
Compared with the prior art, the invention has the following beneficial effects:
the electromagnetic shielding optical cable prepared by the invention comprises a sheath layer, a shielding layer and a cable core from outside to inside; the sheath layer is epoxy resin added with modified graphite aerogel; the shielding layer comprises a melamine foam layer, a foam metal layer and carbon fibers;
the modified graphite aerogel is prepared by introducing pyrrolidone microspheres between graphene layers; the pyrrolidone microspheres are prepared by reacting maleic anhydride, N-vinyl pyrrolidone and vinyl cyclohexyl ether, the surfaces of the pyrrolidone microspheres contain anhydride and lactam groups, the interior of the pyrrolidone microspheres is of a cross-linked structure, and the heat resistance of the sheath layer is enhanced after epoxy resin is added; the pyrrolidone microspheres are attached to the graphene, so that the modified graphite aerogel has a porous structure and a three-dimensional network structure which is connected with each other, the external force can be dispersed, the mechanical strength of the sheath layer is improved, and the modified graphite aerogel also has electromagnetic shielding performance; the modified graphite aerogel between the sheath layer and the shielding layer can react with the melamine foam layer to tightly connect the sheath layer and the shielding layer, so that the strength of the optical cable is enhanced;
the shielding layer is prepared by depositing foam metal on the surface of the carbon fiber and then coating the foam etherified melamine resin; coating a molecular film containing oxygen and nitrogen groups on the surface of carbon fiber precursor prepared by polyacrylonitrile wet spinning, carrying out pre-oxidation in a hydrothermal reaction kettle, adding nickel sulfate, hydrazine hydrate and hexadecyl trimethyl ammonium bromide, carrying out in-situ reduction on the surface of the carbon fiber to generate foamed metallic nickel, coating melamine formaldehyde resin etherified by hexafluorobutanol on the surface, and foaming to form a melamine foam layer; glutamic acid introduces carboxyl on the surface of carbon fiber and forms a molecular film containing oxygen and nitrogen groups, during pre-oxidation, the carbon fiber can adsorb nickel ions and metal nickel with a foam cubic crystal structure generated by surface in-situ reduction, the foam metal nickel is tightly adsorbed on the surface of the molecular film containing oxygen and nitrogen groups, and the added hexadecyl trimethyl ammonium bromide forms an ion layer on the surface of nickel particles, so that the agglomeration of the metal nickel particles is prevented, the average diameter of a chain is reduced, the porosity of the foam metal nickel is increased, electromagnetic waves can be reflected in holes inside a shielding layer, and the electromagnetic shielding performance of the optical cable is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the electro-magnetically shielded optical cable prepared in the examples and comparative examples is as follows:
heat resistance: the examples and comparative examples are subjected to a limiting oxygen index test with reference to GB/T2406;
mechanical properties: the examples and comparative examples were tested for elongation at break and tensile strength with reference to GB/T2951.42.
Electromagnetic shielding property: the examples and comparative examples were subjected to an electromagnetic wave shielding effectiveness test with reference to GB/T30142.
Example 1
(1) Mixing maleic anhydride, azodiisobutyronitrile and freon 225 according to the mass ratio of 2:0.15:10, sequentially adding N-vinyl pyrrolidone of which the mass is 0.8 time that of the maleic anhydride, vinyl cyclohexyl ether of which the mass is 0.5 time that of the maleic anhydride and divinylbenzene which is a crosslinking agent of which the mass is 0.02 time that of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 60 ℃ under the nitrogen atmosphere, reacting for 6 hours, performing ultrasonic dispersion for 2min at 100kHz, performing Soxhlet purification for 36 hours by using acetone, and finally drying in a vacuum drying oven at 45 ℃ to obtain pyrrolidone microspheres; dispersing graphene oxide in deionized water with the mass 30 times that of the graphene oxide, ultrasonically dispersing for 20min at 100kHz, adding pyrrolidone microspheres with the mass 0.25 time that of the graphene oxide, continuously ultrasonically dispersing for 20min, transferring to a hydrothermal reaction kettle, reacting for 12h at 180 ℃, freeze-drying in a freeze dryer at-50 ℃, and finally thermally treating for 2h at 800 ℃ to prepare modified graphite aerogel;
(2) mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 1:10, heating to 85 ℃, mixing for 0.5h under the assistance of 200W microwaves, adding glycerol with the mass of 0.1 time of that of the polyacrylonitrile and thiourea with the mass of 0.05 time of that of the polyacrylonitrile, uniformly mixing to prepare spinning solution, and carrying out wet electrostatic spinning at 70 ℃ and the solidification temperature of 5 ℃ to prepare carbon fiber precursor; dispersing nickel acetate in deionized water with the mass of 30 times that of nickel acetate, uniformly stirring, adding hydrazine hydrate with the mass fraction of 80 percent which is 3 times that of the nickel acetate, and stirring at 30rpm for 0.5h to prepare a nickel acetate solution; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 60%, heating to 80 ℃ for reaction for 1h, fishing out, washing with deionized water for 3min, wiping to dry, stretching to the diameter of 0.06mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 3% which is 5 times that of the carbon fiber precursors, heating to 160 ℃ for reaction for 0.5h, adding a nickel acetate solution with the mass of 20 times that of the carbon fiber precursors and hexadecyl trimethyl ammonium bromide with the mass of 0.15 time that of the carbon fiber precursors, continuing to react for 6h, transferring to a carbonization furnace, and carbonizing at 500 ℃ for 3h under the nitrogen atmosphere to prepare carbon fibers with a foam metal layer;
(3) mixing melamine, paraformaldehyde and triethylamine according to the mass ratio of 1:6:20, heating to 90 ℃, continuously preserving heat for 1h after complete dissolution, adding hexafluorobutanol with the mass of 0.15 time of that of the melamine, adjusting the pH to 5.2 by using nitric acid, keeping the temperature at 90 ℃, reacting for 12h, and adjusting the pH to 8 by using triethylamine to prepare etherified melamine; soaking carbon fibers with a foam metal layer in etherified melamine, adding sodium dodecyl benzene sulfonate which is 0.01 time of the mass of the etherified melamine, stirring for 2min at 2000rpm, adding a foaming agent n-pentane which is 0.02 time of the mass of the etherified melamine and a catalyst oxalic acid which is 0.08 time of the mass of the etherified melamine, continuously stirring for 5s, taking out the carbon fibers with the foam metal layer, coating an optical fiber with the diameter of 0.2mm, placing the optical fiber in a mold which is preheated at 90 ℃ for 3min, sealing and placing the mold in a carbon fiber oven with the foam metal layer for foaming and curing, taking out the carbon fibers after 2h, and finally drying the carbon fibers in a drying oven for 24h to prepare a cable core with a shielding layer, wherein the thickness of the shielding layer is 0.1 mm;
(4) mixing the modified graphite aerogel, the polyamide and the epoxy resin according to the mass ratio of 2:0.5:6, putting the mixture into a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying oven, and drying the mixture for 5 hours at the temperature of 60 ℃ to obtain the electromagnetic shielding optical cable.
Example 2
(1) Mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 3:0.18:13, sequentially adding N-vinyl pyrrolidone 1.1 times of the mass of the maleic anhydride, vinyl cyclohexyl ether 0.6 times of the mass of the maleic anhydride and divinylbenzene as a crosslinking agent 0.04 times of the mass of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 61 ℃ under the nitrogen atmosphere, reacting for 7 hours, performing ultrasonic dispersion for 4min at 150kHz, performing Soxhlet purification for 42 hours by using acetone, and finally drying in a vacuum drying oven at 50 ℃ to obtain pyrrolidone microspheres; dispersing graphene oxide in deionized water with the mass 40 times that of the graphene oxide, ultrasonically dispersing for 25min at 130kHz, adding pyrrolidone microspheres with the mass 0.3 time that of the graphene oxide, continuously ultrasonically dispersing for 25min, transferring to a hydrothermal reaction kettle, reacting for 14h at 190 ℃, freeze-drying in a freeze dryer at-55 ℃, and finally thermally treating for 2h at 850 ℃ to obtain modified graphite aerogel;
(2) mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 2:10, heating to 90 ℃, mixing for 0.5h under the assistance of 250W microwaves, adding glycerol with the mass of 0.15 time of that of the polyacrylonitrile and thiourea with the mass of 0.01 time of that of the polyacrylonitrile, uniformly mixing to prepare spinning solution, and carrying out wet electrostatic spinning at 80 ℃ and the solidification temperature of 10 ℃ to prepare carbon fiber precursor; dispersing nickel acetate in deionized water with the mass of 35 times that of the nickel acetate, uniformly stirring, adding hydrazine hydrate with the mass fraction of 83 percent which is 4 times that of the nickel acetate, and stirring at 40rpm for 0.5h to prepare a nickel acetate solution; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 65%, heating to 85 ℃, reacting for 1h, fishing out, washing with deionized water for 4min, wiping to dry, stretching to the diameter of 0.07mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 4% which is 7 times that of the carbon fiber precursors, heating to 170 ℃, reacting for 0.5h, adding a nickel acetate solution with the mass of 23 times that of the carbon fiber precursors and hexadecyl trimethyl ammonium bromide with the mass of 0.2 time that of the carbon fiber precursors, continuing to react for 7h, transferring to a carbonization furnace, and carbonizing for 4h at 700 ℃ in a nitrogen atmosphere to prepare the carbon fibers with the foam metal layer;
(3) mixing melamine, paraformaldehyde and triethylamine according to a mass ratio of 1:7:30, heating to 94 ℃, keeping the temperature for 1h after complete dissolution, adding hexafluorobutanol with the mass of 0.22 time of that of the melamine, adjusting the pH to 5.4 by using nitric acid, keeping the temperature at 93 ℃, reacting for 18h, and adjusting the pH to 8.5 by using triethylamine to prepare etherified melamine; soaking carbon fibers with a foam metal layer in etherified melamine, adding sodium dodecyl benzene sulfonate which is 0.03 time of the mass of the etherified melamine, stirring for 4min at 2200rpm, adding a foaming agent n-pentane which is 0.03 time of the mass of the etherified melamine and a catalyst oxalic acid which is 0.09 time of the mass of the etherified melamine, continuously stirring for 6s, taking out the carbon fibers with the foam metal layer, coating an optical fiber with the diameter of 0.3mm, placing the optical fiber in a mold which is preheated for 4min at 95 ℃, sealing and placing the mold in a carbon fiber oven with the foam metal layer for foaming and curing, taking out the carbon fibers after 2.5h, and finally drying the carbon fibers in the oven for 36h to prepare a cable core with a shielding layer, wherein the thickness of the shielding layer is 0.5 mm;
(4) mixing the modified graphite aerogel, the polyamide and the epoxy resin according to the mass ratio of 2:0.6:7, putting the mixture into a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying oven, and drying the mixture for 5 hours at 70 ℃ to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 335 ℃ and the thickness of a sheath layer is 0.1 mm.
Example 3
(1) Mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 4:0.2:15, sequentially adding N-vinyl pyrrolidone 1.2 times the mass of the maleic anhydride, vinyl cyclohexyl ether 0.8 times the mass of the maleic anhydride and divinylbenzene 0.05 times the mass of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 62 ℃ under the nitrogen atmosphere, reacting for 8 hours, performing ultrasonic dispersion for 3min at 200kHz, performing Soxhlet purification for 48 hours by using acetone, and finally drying in a vacuum drying oven at 55 ℃ to obtain pyrrolidone microspheres; dispersing graphene oxide in deionized water with the mass of 50 times that of the graphene oxide, ultrasonically dispersing for 30min at 150kHz, adding pyrrolidone microspheres with the mass of 0.35 time that of the graphene oxide, continuously ultrasonically dispersing for 30min, transferring to a hydrothermal reaction kettle, reacting for 16h at 200 ℃, freeze-drying in a freeze dryer at-60 ℃, and finally thermally treating for 3h at 900 ℃ to obtain modified graphite aerogel;
(2) mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 3:10, heating to 100 ℃, mixing for 1h under the assistance of 300W microwaves, adding glycerol with the mass of 0.2 time of that of polyacrylonitrile and thiourea with the mass of 0.15 time of that of polyacrylonitrile, uniformly mixing to prepare spinning solution, and carrying out wet electrostatic spinning at 90 ℃ at a solidification temperature of 15 ℃ to prepare carbon fiber precursor; dispersing nickel acetate in deionized water 40 times of the mass of the nickel acetate, uniformly stirring, adding hydrazine hydrate 85% in a mass fraction 5 times of the mass of the nickel acetate, and stirring at 50rpm for 1h to prepare a nickel acetate solution; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 70%, heating to 90 ℃ for reaction for 2h, fishing out, washing with deionized water for 5min, wiping and stretching to the diameter of 0.08mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 5% which is 10 times that of the carbon fiber precursors, heating to 180 ℃ for reaction for 1h, adding a nickel acetate solution with the mass of 25 times that of the carbon fiber precursors and hexadecyl trimethyl ammonium bromide with the mass of 0.25 time that of the carbon fiber precursors, continuing to react for 8h, transferring to a carbonization furnace, and carbonizing at 1000 ℃ for 35h under the nitrogen atmosphere to obtain carbon fibers with a foam metal layer;
(3) mixing melamine, paraformaldehyde and triethylamine according to the mass ratio of 1:8:40, heating to 95 ℃, continuously preserving heat for 2 hours after complete dissolution, adding hexafluorobutanol with the mass of 0.3 time of that of the melamine, adjusting the pH to 5.5 by using nitric acid, keeping the temperature at 95 ℃, reacting for 24 hours, and adjusting the pH to 9 by using triethylamine to prepare etherified melamine; soaking carbon fibers with a foam metal layer in etherified melamine, adding sodium dodecyl benzene sulfonate which is 0.04 times of the mass of the etherified melamine, stirring for 5min at 2500rpm, adding a foaming agent n-pentane which is 0.04 times of the mass of the etherified melamine and a catalyst oxalic acid which is 0.1 times of the mass of the etherified melamine, continuously stirring for 8s, taking out the carbon fibers with the foam metal layer, coating an optical fiber with the diameter of 0.5mm, placing the optical fiber in a mold which is preheated for 5min at 100 ℃, sealing and placing the mold in a carbon fiber oven with the foam metal layer for foaming and curing, taking out the carbon fibers after 3h, and finally drying the carbon fibers in a drying oven for 48h to prepare a cable core with a shielding layer, wherein the thickness of the shielding layer is 0.2 mm;
(4) mixing the modified graphite aerogel, the polyamide and the epoxy resin according to the mass ratio of 3:0.8:8, putting the mixture into a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying oven, and drying the mixture for 6 hours at 80 ℃ to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 355 ℃ and the thickness of a sheath layer is 0.15 mm.
Comparative example 1
The formulation of comparative example 1 was the same as that of example 2. The preparation method of the electromagnetic shielding optical cable is different from the embodiment 2 only in the difference of the step (1), and the step (1) is modified as follows: dispersing graphene oxide in deionized water with the mass 40 times that of the graphene oxide, ultrasonically dispersing for 50min at 130kHz, transferring to a hydrothermal reaction kettle, reacting for 14h at 190 ℃, freeze-drying in a freeze dryer at-55 ℃, and finally performing heat treatment for 2h at 850 ℃ to obtain the modified graphite aerogel.
Comparative example 2
Comparative example 2 was formulated in the same manner as in example 2. The preparation method of the electromagnetic shielding optical cable is different from the embodiment 2 only in the steps (1) and (4), and the steps (1) and (4) are modified as follows: (1) mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 3:0.18:13, sequentially adding N-vinyl pyrrolidone 1.1 times of the mass of the maleic anhydride, vinyl cyclohexyl ether 0.6 times of the mass of the maleic anhydride and divinylbenzene as a crosslinking agent 0.04 times of the mass of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 61 ℃ under the nitrogen atmosphere, reacting for 7 hours, performing ultrasonic dispersion for 4min at 150kHz, performing Soxhlet purification for 42 hours by using acetone, and finally drying in a vacuum drying oven at 50 ℃ to obtain pyrrolidone microspheres; dispersing graphene oxide in deionized water with the mass 40 times that of the graphene oxide, ultrasonically dispersing for 50min at 130kHz, transferring to a hydrothermal reaction kettle, reacting for 14h at 190 ℃, freeze-drying in a freeze dryer at-55 ℃, and finally performing heat treatment for 2h at 850 ℃ to obtain modified graphite aerogel; (4) mixing pyrrolidone microspheres, modified graphite aerogel, polyamide and epoxy resin according to a mass ratio of 0.5:1.5:0.6:7, putting the mixture into a screw extruder, carrying out melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying oven, and drying the mixture at 70 ℃ for 5 hours to obtain the electromagnetic shielding optical cable.
Comparative example 3
The formulation of comparative example 3 was the same as that of example 2. The preparation method of the electromagnetic shielding optical cable is different from that of the embodiment 2 only in that the treatment of the step (1) is not performed, and the step (4) is modified as follows: mixing polyamide and epoxy resin according to a mass ratio of 0.6:7, placing the mixture in a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture to a drying oven, and drying the mixture for 5 hours at 70 ℃ to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 335 ℃ and the thickness of a sheath layer is 0.1 mm.
Comparative example 4
Comparative example 4 was formulated as in example 2. The preparation method of the electromagnetic shielding optical cable is different from the embodiment 2 only in the difference of the step (3), and the step (3) is modified as follows: and coating an optical fiber with the diameter of 0.5mm by using the carbon fiber with the foam metal layer to prepare the cable core with the shielding layer, wherein the thickness of the shielding layer is 0.2 mm.
Comparative example 5
The formulation of comparative example 5 was the same as example 2. The preparation method of the electromagnetic shielding optical cable is different from the embodiment 2 only in the difference of the step (2), and the step (2) is modified as follows: mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 2:10, heating to 90 ℃, mixing for 0.5h under the assistance of 250W microwaves, adding glycerol with the mass of 0.15 time of that of the polyacrylonitrile and thiourea with the mass of 0.01 time of that of the polyacrylonitrile, uniformly mixing to prepare spinning solution, and carrying out wet electrostatic spinning at 80 ℃ and the solidification temperature of 10 ℃ to prepare carbon fiber precursor; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 65%, heating to 85 ℃, reacting for 1h, fishing out, washing with deionized water for 4min, wiping, stretching to the diameter of 0.07mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 4% which is 7 times that of the carbon fiber precursors, heating to 170 ℃, reacting for 0.5h, transferring to a carbonization furnace, and carbonizing for 4h at 700 ℃ in a nitrogen atmosphere to obtain the carbon fibers with the foam metal layer.
Comparative example 6
(1) Mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 3:0.18:13, sequentially adding N-vinyl pyrrolidone 1.1 times of the mass of the maleic anhydride, vinyl cyclohexyl ether 0.6 times of the mass of the maleic anhydride and divinylbenzene as a crosslinking agent 0.04 times of the mass of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 61 ℃ under the nitrogen atmosphere, reacting for 7 hours, performing ultrasonic dispersion for 4min at 150kHz, performing Soxhlet purification for 42 hours by using acetone, and finally drying in a vacuum drying oven at 50 ℃ to obtain pyrrolidone microspheres; dispersing graphene oxide in deionized water with the mass 40 times that of the graphene oxide, performing ultrasonic dispersion for 25min at 130kHz, adding pyrrolidone microspheres with the mass 0.3 time that of the graphene oxide, continuing performing ultrasonic dispersion for 25min, transferring the mixture to a hydrothermal reaction kettle, reacting for 14h at 190 ℃, performing freeze drying in a freeze dryer at-55 ℃, and finally performing heat treatment for 2h at 850 ℃ to obtain modified graphite aerogel;
(2) mixing the modified graphite aerogel, the polyamide and the epoxy resin according to the mass ratio of 2:0.6:7, putting the mixture into a screw extruder, performing melt extrusion on the surface of an optical fiber with the diameter of 0.5mm, transferring the mixture to a drying oven, and drying the mixture for 5 hours at 70 ℃ to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 335 ℃ and the thickness of a sheath layer is 0.1 mm.
Examples of effects
Table 1 below shows the results of performance analysis of the electro-magnetically shielded optical cables according to examples 1, 2 and 3 of the present invention and comparative examples 1, 2, 3, 4, 5 and 6.
TABLE 1
Compared with experimental data of the embodiment and the comparative example in the table 1, it can be obviously found that the electromagnetic shielding optical cables prepared in the embodiments 1, 2 and 3 have better heat resistance, mechanical property and electromagnetic shielding property;
the experimental data comparison of the examples 1, 2 and 3 and the comparative examples 1, 2 and 3 shows that the modified graphite aerogel prepared by introducing pyrrolidone microspheres between graphene layers has a cross-linked structure inside, and the heat resistance of the sheath layer is enhanced after the epoxy resin is added, so that the modified graphite aerogel has a porous structure and a three-dimensional network structure connected with each other, the mechanical strength of the sheath layer is improved, the electromagnetic shielding performance is achieved, and the sheath layer is tightly connected with the shielding layer, so that the strength of the optical cable is enhanced; from the comparison of experimental data of examples 1, 2 and 3 and comparative examples 4, 5 and 6, it can be found that the electromagnetic wave can be reflected in the holes inside the shielding layer by depositing the foam metal on the surface of the carbon fiber and then coating the shielding layer made of the foamed etherified melamine resin, thereby enhancing the electromagnetic shielding performance of the optical cable.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. An electromagnetic shielding optical cable comprises a sheath layer, a shielding layer and a cable core from outside to inside, and is characterized in that the sheath layer is modified graphite aerogel; the cable core is an optical fiber.
2. The electromagnetic shielding optical cable according to claim 1, wherein the modified graphite aerogel is prepared by introducing pyrrolidone microspheres between graphene layers; the pyrrolidone microspheres are prepared by reacting maleic anhydride, N-vinyl pyrrolidone and vinyl cyclohexyl ether.
3. The electromagnetically shielded optical cable as claimed in claim 1, wherein the shielding layer comprises a melamine foam layer, a foam metal layer and carbon fibers.
4. The electromagnetic shielding optical cable according to claim 3, wherein the carbon fiber is prepared by performing pre-oxidation and carbonization after polyacrylonitrile is subjected to wet spinning; the foam metal layer is prepared by carrying out in-situ reduction on the carbon fiber by nickel sulfate, hydrazine hydrate and hexadecyl trimethyl ammonium bromide; the melamine foam layer is prepared by coating hexafluorobutanol etherified melamine formaldehyde resin outside a foam metal layer and foaming.
5. The preparation method of the electromagnetic shielding optical cable is characterized by comprising the following specific steps of:
(1) dispersing graphene oxide in deionized water with the mass of 30-50 times that of the graphene oxide, ultrasonically dispersing for 20-30 min at 100-150 kHz, adding pyrrolidone microspheres with the mass of 0.25-0.35 time that of the graphene oxide, continuously ultrasonically dispersing for 20-30 min, transferring to a hydrothermal reaction kettle, reacting for 12-16 h at 180-200 ℃, freeze-drying in a freeze dryer at-50-60 ℃, and finally performing heat treatment for 2-3 h at 800-900 ℃ to obtain modified graphite aerogel;
(2) dispersing nickel acetate in deionized water with the mass 30-40 times that of the nickel acetate, uniformly stirring, adding hydrazine hydrate with the mass fraction of 80-85% which is 3-5 times that of the nickel acetate, and stirring at 30-50 rpm for 0.5-1 h to prepare a nickel acetate solution; soaking carbon fiber precursors in a nitric acid solution with the mass fraction of 60-70%, heating to 80-90 ℃, reacting for 1-2 h, fishing out, washing with deionized water for 3-5 min, wiping dry, stretching to the diameter of 0.06-0.08 mm, transferring to a hydrothermal reaction kettle, adding a glutamic acid solution with the mass fraction of 3-5% which is 5-10 times that of the carbon fiber precursors, heating to 160-180 ℃, reacting for 0.5-1 h, adding a nickel acetate solution with the mass of 20-25 times that of the carbon fiber precursors and hexadecyl trimethyl ammonium bromide with the mass of 0.15-0.25 time that of the carbon fiber precursors, continuing to react for 6-8 h, transferring to a carbonization furnace, carbonizing at 500-1000 ℃ for 3-5 h under the nitrogen atmosphere, and preparing carbon fibers with foam metal layers;
(3) soaking carbon fibers with a foam metal layer in etherified melamine, adding sodium dodecyl benzene sulfonate which is 0.01-0.04 times of the mass of the etherified melamine, stirring at 2000-2500 rpm for 2-5 min, adding a foaming agent n-pentane which is 0.02-0.04 times of the mass of the etherified melamine and a catalyst oxalic acid which is 0.08-0.1 times of the mass of the etherified melamine, continuously stirring for 5-8 s, taking out the carbon fibers with the foam metal layer, coating a cable core, placing the cable core in a mold which is preheated at 90-100 ℃ for 3-5 min, sealing, placing the mold in a carbon fiber oven with the foam metal layer for foaming and curing, taking out the cable core after 2-3 h, and finally drying the cable core in a drying box for 24-48 h to obtain the cable core with the shielding layer;
(4) mixing the modified graphite aerogel, polyamide and epoxy resin according to a mass ratio of 2:0.5: 6-3: 0.8:8, putting the mixture into a screw extruder, performing melt extrusion on the surface of a cable core with a shielding layer, transferring the mixture into a drying box, and drying the mixture at the temperature of 60-80 ℃ for 5-6 hours to obtain the electromagnetic shielding optical cable, wherein the melt temperature is 315-355 ℃, and the thickness of a sheath layer is 0.05-0.15 mm.
6. The method for preparing an electromagnetically shielded optical cable as claimed in claim 5, wherein in the step (1): the preparation method of the pyrrolidone microspheres comprises the following steps: mixing maleic anhydride, azobisisobutyronitrile and freon 225 according to the mass ratio of 2:0.15: 10-4: 0.2:15, sequentially adding N-vinyl pyrrolidone of which the mass is 0.8-1.2 times that of the maleic anhydride, vinyl cyclohexyl ether of which the mass is 0.5-0.8 times that of the maleic anhydride and cross-linking agent divinylbenzene of which the mass is 0.02-0.05 times that of the maleic anhydride, stirring until the solution is clear, introducing nitrogen to replace air, heating to 60-62 ℃ under the nitrogen atmosphere, reacting for 6-8 hours, ultrasonically dispersing for 2-3 minutes under 100-200 kHz, performing Soxhlet purification for 36-48 hours by using acetone, and finally drying in a vacuum drying oven at 45-55 ℃ to obtain the pyrrolidone microspheres.
7. The method for preparing an electromagnetically shielded optical cable as claimed in claim 5, wherein in the step (2): the preparation method of the carbon fiber precursor comprises the following steps: mixing polyacrylonitrile and dimethyl diamide according to a mass ratio of 1: 10-3: 10, heating to 85-100 ℃, mixing for 0.5-1 h under the assistance of 200-300W microwaves, adding glycerol 0.1-0.2 time of the mass of the polyacrylonitrile and thiourea 0.05-0.15 time of the mass of the polyacrylonitrile, uniformly mixing to prepare a spinning solution, and performing wet electrostatic spinning at 70-90 ℃ with a solidification temperature of 5-15 ℃ to prepare the carbon fiber precursor.
8. The method for preparing an electromagnetically shielded optical cable as claimed in claim 5, wherein in the step (3): the preparation method of the etherified melamine comprises the following steps: mixing melamine, paraformaldehyde and triethylamine according to the mass ratio of 1:6: 20-1: 8:40, heating to 90-95 ℃, continuously preserving heat for 1-2 hours after complete dissolution, adding hexafluorobutanol with the mass of 0.15-0.3 times of that of the melamine, adjusting the pH value to 5.2-5.5 with nitric acid, keeping the temperature at 90-95 ℃, reacting for 12-24 hours, and adjusting the pH value to 8-9 with triethylamine to obtain the etherified melamine.
9. The method for preparing an electromagnetically shielded optical cable as claimed in claim 5, wherein in the step (3): the cable core is an optical fiber with the diameter of 0.2-0.5 mm.
10. The method for preparing an electromagnetically shielded optical cable as claimed in claim 5, wherein in the step (4): the thickness of the shielding layer is 0.1-0.2 mm.
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