CN110029502B - Method for preparing color carbon fiber material based on electropolymerization technology - Google Patents
Method for preparing color carbon fiber material based on electropolymerization technology Download PDFInfo
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- CN110029502B CN110029502B CN201910303347.6A CN201910303347A CN110029502B CN 110029502 B CN110029502 B CN 110029502B CN 201910303347 A CN201910303347 A CN 201910303347A CN 110029502 B CN110029502 B CN 110029502B
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- carbon fiber
- electropolymerization
- epoxy resin
- preparing
- material based
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 128
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 128
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000005516 engineering process Methods 0.000 title claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- -1 glycidyl ester Chemical class 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229960000834 vinyl ether Drugs 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- GVXHSMAJJFVLGD-UHFFFAOYSA-N methyl 5-chloro-7-(trifluoromethyl)thieno[3,2-b]pyridine-3-carboxylate Chemical compound C1=C(Cl)N=C2C(C(=O)OC)=CSC2=C1C(F)(F)F GVXHSMAJJFVLGD-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 4
- JOTQIXXCBHIDKJ-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidine Chemical compound CCN1CCN(C)C1 JOTQIXXCBHIDKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- CCZXMDQFIVMWMF-UHFFFAOYSA-N trifluoromethoxyboronic acid Chemical compound OB(O)OC(F)(F)F CCZXMDQFIVMWMF-UHFFFAOYSA-N 0.000 claims description 3
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 239000012952 cationic photoinitiator Substances 0.000 claims description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 239000003973 paint Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000003086 colorant Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- BLMPUZAOLNGPQT-UHFFFAOYSA-N cyclohexylmethyl formate Chemical compound O=COCC1CCCCC1 BLMPUZAOLNGPQT-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- CGRJJOYCFCCGPX-UHFFFAOYSA-N 3-ethyloxetane Chemical compound CCC1COC1 CGRJJOYCFCCGPX-UHFFFAOYSA-N 0.000 description 1
- DHDPUVPGALXWOL-UHFFFAOYSA-N 3-methyloxetan-3-ol Chemical compound CC1(O)COC1 DHDPUVPGALXWOL-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—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
- 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
- D06M15/55—Epoxy resins
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a method for preparing a colored carbon fiber material based on an electropolymerization technology, which relates to the technical field of carbon fibers, and is provided for solving the problems that carbon fibers are black, low in surface energy, difficult to modify the surface, difficult to coat and color-endow common ink and paint and the like due to chemical composition and structural characteristics of the carbon fibers, and comprises the following steps: (1) cleaning the surface of the carbon fiber; (2) preparing an electropolymerized ink system; (3) an electropolymerization process; (4) the fiber is treated after electropolymerization. The invention has the beneficial effects that: the surface of the carbon fiber is modified by utilizing an electric polymerization technology, the colored carbon fiber can be prepared, various colors are given to the carbon fiber, the application field of the carbon fiber is widened, and the preparation process and the operation are simple.
Description
Technical Field
The invention relates to the technical field of carbon fiber materials, in particular to a method for preparing a color carbon fiber material based on an electropolymerization technology.
Background
The carbon fiber is a high-strength and high-modulus fiber which is obtained by carbonizing and graphitizing organic fibers such as flake graphite microcrystals and has a carbon content of 95% or more. The fiber has many excellent properties, high axial strength and modulus, low density, high specific performance, no creep deformation, super high temperature resistance in non-oxidation environment, good fatigue resistance, specific heat and conductivity between nonmetal and metal, small thermal expansion coefficient, anisotropy, good corrosion resistance, good X-ray permeability, good electric and heat conductivity, good electromagnetic shielding property and the like, is a new generation of reinforced fiber, and is an important material in national defense, military industry and civil use.
The carbon fiber is graphitized fiber and has inherent characteristics of a carbon material, for example, the carbon fiber only presents single black color, if a carbon fiber product with other colors is obtained, only painting covering treatment can be carried out on the surface of the carbon fiber composite material, and the service performance of the carbon fiber composite material can be influenced by the paint film in color covering, the adhesion of the paint film to the surface of the composite material, the mechanical property of the paint film and the like, so that the carbon fiber material is limited in civil use.
Since carbon fibers are almost materials composed of carbon, the surface energy is low, the interfacial bonding property with other materials is poor, and the diameter of carbon fibers is small, there are many problems in changing the color thereof by the surface coating method: the colored paint is difficult to fix on the surface, and the binding force is poor; the traditional coating method has thick paint film, changes the size of the carbon fiber and the performance of the fiber; uniform coating is difficult and the operation process is complicated … …. therefore, the carbon fiber surface modification technology is always in a blank state and the preparation of colored carbon fibers is also always in a blank state for various reasons.
Disclosure of Invention
The invention aims to solve the problems of surface modification of the carbon fiber, endowing the carbon fiber with colorful colors, simultaneously improving the surface performance of the carbon fiber and widening the application field of the carbon fiber.
The invention adopts the following technical scheme to solve the technical problems: a method for preparing a colored carbon fiber material based on an electropolymerization technology comprises the following steps:
(1) cleaning the surface of the carbon fiber: cleaning and impurity removing carbon fiber tows and drying;
(2) preparation of a color electropolymerization system: taking a monomer and a toner, adding an initiator, and mixing and stirring uniformly;
(3) and (3) electropolymerization: preparing the carbon fiber tows treated in the step (1) into filamentous carbon fibers, intensively fixing one end of each filamentous carbon fiber at a power supply anode, immersing the other end of each filamentous carbon fiber into the electropolymerization system prepared in the step (2), and electropolymerizing the carbon fiber tows by using a graphite electrode as a cathode;
(4) fiber electropolymerization post-treatment: and washing and drying the electropolymerized fiber.
Preferably, in the step (1), the carbon fiber tow is soaked in deionized water for ultrasonic cleaning, and then is washed with acetone under reflux, and then is washed with distilled water and dried.
Preferably, the monomer is one or more of epoxy monomers, vinyl ether monomers, epoxy resins, oxetane, thiophene and derivatives thereof, pyrrole and derivatives thereof, pyridine and derivatives thereof, aniline and derivatives thereof.
Preferably, the epoxy monomer is one or more of aliphatic epoxy monomer, glycidyl ether epoxy monomer and glycidyl ester epoxy monomer.
Preferably, the vinyl ether monomer is one or more of propylene oxide benzyl ether, propylene oxide phenyl ether, propenyl glycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether and ethylene glycol divinyl ether.
Preferably, the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, bisphenol a epoxy resin, hydrogenated bisphenol a epoxy resin, brominated epoxy resin, silicone-modified epoxy resin, organic phosphorus epoxy resin, polyurethane epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and novolac epoxy resin.
Preferably, the toner is one or a mixture of organic dye, inorganic dye, organic pigment or inorganic pigment.
Preferably, the mass fraction of the toner is 1-20% of the whole.
Preferably, the cationic photoinitiator is: diphenyliodohexafluorophosphate, 4' -diphenyliodohexafluorophosphate, sulfonium triarylhexafluorophosphate, sulfonium triarylhexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluorophosphate, silver hexafluoroantimonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, tetraphenylphosphonium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluoroantimonate, tris [4- (dibutylamino) phenyl ] ammonium hexafluoroantimonate, 4-octyloxybis (diphenyliodonium hexafluoroantimonate), bis (4-dodecylbenzene) iodonium hexafluoroantimonate, N-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-ethylpyridinium hexafluorophosphate, 1-hexyl-3-methylpyridinium hexafluorophosphate, 1-ethyl-3-methylimidazoline trifluoro (trifluoromethyl) borate, 1-butyl-3-methylimidazoline dibutyl phosphate, 1-butylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, trimethyloxonium hexachloroantimonate triphenyl carbon pentachloronitine stannic acid.
Preferably, the mass of the initiator added in the step (2) is 0.05-5% of the mass of the monomer.
Preferably, in the step (4), the electropolymerized product is washed with deionized water and ethanol and then dried.
The invention has the beneficial effects that:
(1) because the conductive base material is immersed in an electropolymerization system, after electrification, the initiator is initiated on the surface of the base material and decomposed into cations, so that the monomer or resin is initiated to polymerize, and the polymerization extends outwards from the surface of the base material, and the adhesion between the polymer and the base material is very good due to the growth mode. The reason is that the carbon fiber is not only a coated object, but also a conductor for providing electric conduction, electrons are conducted from the surface of the carbon fiber to an initiator which is in contact with the carbon fiber, namely the initiator on the surface of the carbon fiber, the initiator is decomposed on the surface of the carbon fiber to generate anions and cations, the cations can initiate the functional groups such as epoxy and the like adjacent to the carbon fiber on the surface of the carbon fiber to be polymerized and grown, the initiated cations and the epoxy polymerization growth process of the cations are always in a cationic state, and the cations in the initiation and growth processes are always adsorbed on the surface of the carbon fiber due to the principle that a large amount of electrons pass through the surface of the carbon fiber and the cations are attracted by positive and negative electricity.
In addition, the polymerization of monomers into macromolecules has a volume contraction due to the conversion of the van der waals radii between the molecules into chemical bonds, which if not supplemented in time by more monomers, would remain in the coating resulting in very large internal stresses and thus poor adhesion. For example, in photopolymerization, due to the directionality of illumination, polymerization starts from the upper layer solution, the bottom layer, i.e., the surface of the base material, is finally illuminated, and polymerization finally occurs, so that no external monomer is supplemented in the polymerization of the bottom layer, the volume shrinkage is obvious, the internal stress is large, and the adhesive force of the polymer coating film is greatly reduced. In the electropolymerization process of the carbon fiber surface, polymerization starts from the bottom layer, and the upper layer solution can be timely supplemented to the lower layer, so that volume shrinkage is timely supplemented by the solution, the solution is greatly reduced or eliminated, and finally generated polymers have good adhesive force with the carbon fiber surface. When the polymer film grows to a certain thickness (only a few microns), the polymer film becomes an insulating layer, so that the surface of the carbon fiber is not conductive any more, the polymerization is automatically terminated, the thickness of the polymer film layer is not increased any more, the thickness of the film layer can be automatically controlled, and the increase of the fiber size is limited.
(2) Under the action of current, the initiator ionizes anions and cations, and the cations can initiate polymerization of epoxy and vinyl ether monomers. Because electropolymerization starts to initiate the outward growth from the surface of the conductive base material, and in addition, oxygen atoms, hydroxyl groups and the like on the epoxy polymer have better binding force with the surface of the base material, the binding force between the coating and the base material is good.
(3) The carbon fiber has good conductivity, and can be used as a good base material for electropolymerization, so that the electropolymerization can be realized on the surface of the carbon fiber, and the performance of the surface of the carbon fiber is improved.
(4) If the toner is added into the polymerization system, the toner is solidified in the polymer film layer when the monomer is solidified, so that the surface of the carbon fiber is uniformly coated with a layer of color ink, and the surface of the carbon fiber can be changed into different colors by different color inks, thereby enabling the carbon fiber to have various colors.
The method utilizes an electric polymerization technology to carry out electric polymerization on the surface of the carbon fiber material, modify the surface performance of the carbon fiber, prepare the colored carbon fiber, improve the interface bonding force between the carbon fiber and a composite material matrix and widen the application field of the carbon fiber; the method has simple process flow and operation and remarkable effect.
Detailed Description
The present invention will now be described in further detail.
The experimental procedures in the following examples are conventional unless otherwise specified.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. 0.25 g of initiator 1-hexyl-3-methylpyridine hexafluorophosphate, 40 g of 3,3' - (oxybis methylene) bis (3-ethyl) oxetane and 10 g of white titanium black are taken, stirred and dispersed evenly. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 5V, and setting the polymerization time to be 5 min; a white coating was obtained on the surface of the carbon fibers. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the white carbon fiber.
Example 2
Taking 15 g of carbon fiber, ultrasonically cleaning the carbon fiber by using water, acetone and water in sequence, and drying the carbon fiber. Taking 1 g of initiator trimethyl oxonium hexachloroantimonate triphenyl carbon pentachlorocystanoic stannic acid, 20 g of bisphenol A epoxy resin, 20 g of oxetane, 5 g of white titanium black and 5 g of phthalocyanine blue, and stirring and dispersing uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 10V, and setting the polymerization time to be 4 min; a blue coating was obtained on the surface of the carbon fibers. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the blue carbon fiber.
Example 3
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. 1.5 g of initiator tetraphenylphosphonium hexafluoroantimonate, 20 g of bisphenol A epoxy resin, 20 g of 3-methyl-3-hydroxymethyl oxetane, 4 g of white titanium black and 6 g of iron oxide red are taken, stirred and dispersed uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 15V, and setting the polymerization time to be 3 min; a red coating was obtained on the carbon fiber surface. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the red carbon fiber.
Example 4
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. 2 g of initiator 1-ethyl-3-methylimidazoline trifluoro (trifluoromethyl) borate, 25 g of 1, 4-dicyclohexyl dimethyl divinyl ether, 15 g of 2-perfluoropropoxy perfluoropropyl trifluoro vinyl ether bisphenol A epoxy resin, 4 g of white titanium black and 6 g of lemon yellow are taken, stirred and dispersed uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 30V, and setting the polymerization time to be 3 min; a yellow coating was obtained on the surface of the carbon fibers. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the yellow carbon fiber.
Example 5
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. Taking 3 g of initiator tetraphenylphosphonium hexafluoroantimonate, (3, 4-epoxy group) cyclohexyl methyl formate (3, 4-epoxy group) 25 g, 3-hydroxy-3-methyl oxetane 15 g, white titanium black 5 g and cobalt green pigment 5 g, and stirring and dispersing uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 40V, and setting the polymerization time to be 2.5 min; a green coating was obtained on the carbon fiber surface. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the green carbon fiber.
Example 6
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. Taking 2.5 g of initiator tris [4- (dibutylamino) phenyl ] ammonium hexafluoroantimonate, (3, 4-epoxy group) cyclohexyl methyl formate (3, 4-epoxy group) 25 g, thiophene 15 g, white titanium black 18 g, carbon black 1 g and iron oxide red 1 g, stirring and dispersing uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 50V, and setting the polymerization time to be 2 min; a light grey coating is obtained on the surface of the carbon fibre. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the light gray carbon fiber.
Example 7
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. Taking 2 g of 1-butylpyridinium tetrafluoroborate as an initiator, 25 g of polyurethane epoxy resin, 15 g of 1-tert-butoxycarbonyl-L-azetidine-2-formic acid, 3 g of silicon dioxide and 15 g of aluminum powder, and uniformly stirring and dispersing to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 75V, and setting the polymerization time to be 1 min; and obtaining a metallic silver coating on the surface of the carbon fiber. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the metallic silvery carbon fiber.
Example 8
10 g of carbon fiber is taken, washed by water, acetone and water in sequence by ultrasonic and then dried. Taking 2 g of initiator tris [4- (dibutylamino) phenyl ] ammonium hexafluoroantimonate, 15 g of bisphenol A diglycidyl ether (DGEBPA) epoxy resin, 25 g of 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate, 3 g of silicon dioxide and 15 g of copper powder, and stirring and dispersing uniformly to obtain a mixed solution. Fixing one end of the carbon fiber bundle on the positive electrode of a direct current stabilized power supply, placing the other end of the carbon fiber bundle in the solution, connecting the negative electrode of the direct current stabilized power supply with a commercially available graphite electrode, placing the carbon fiber bundle in the solution, setting the output voltage of the direct current stabilized power supply to be 65V, and setting the polymerization time to be 2 min; and obtaining a metallic copper coating on the surface of the carbon fiber. And respectively washing the surface of the coating by using absolute ethyl alcohol and deionized water to obtain the metallic copper-colored carbon fiber.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A method for preparing a colored carbon fiber material based on an electropolymerization technology is characterized by comprising the following steps: the method comprises the following steps:
(1) cleaning the surface of the carbon fiber: cleaning and impurity removing carbon fiber tows and drying;
(2) preparation of a color electropolymerization system: taking a monomer and a toner, adding an initiator, mixing and stirring to obtain an electropolymerization system;
(3) and (3) electropolymerization: preparing the carbon fiber tows treated in the step (1) into filamentous carbon fibers, intensively fixing one end of each filamentous carbon fiber at a power supply anode, immersing the other end of each filamentous carbon fiber into the electropolymerization system prepared in the step (2), and electropolymerizing the carbon fiber tows by using a graphite electrode as a cathode;
(4) fiber electropolymerization post-treatment: and washing and drying the electropolymerized fiber.
2. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 1, wherein: the toner is one or a mixture of organic dye, inorganic dye, organic pigment or inorganic pigment and metal powder.
3. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 2, characterized in that: the content of the toner is 1-20 wt% of the whole electropolymerization system.
4. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 1, wherein: in the step (1), the carbon fiber tows are soaked in deionized water for ultrasonic cleaning, then acetone is adopted for reflux cleaning, and then distilled water is used for cleaning and drying.
5. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 1, wherein: the monomer is one or more of epoxy monomers, vinyl ether monomers, epoxy resin, oxetane, thiophene and derivatives thereof, pyrrole and derivatives thereof, pyridine and derivatives thereof, and aniline and derivatives thereof.
6. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 5, wherein: the epoxy monomer is one or more of aliphatic epoxy monomer, glycidyl ether epoxy monomer and glycidyl ester epoxy monomer.
7. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 5, wherein: the vinyl ether monomer is one or more of epoxypropane benzyl ether, epoxypropane phenyl ether, propenyl glycidyl ether, ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether and ethylene glycol divinyl ether.
8. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 5, wherein: the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated epoxy resin, organic silicon modified epoxy resin, organic phosphorus epoxy resin, polyurethane epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and novolac epoxy resin.
9. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 1, wherein: the cationic photoinitiator is as follows: diphenyliodohexafluorophosphate, 4' -diphenyliodohexafluorophosphate, sulfonium triarylhexafluorophosphate, sulfonium triarylhexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluorophosphate, silver hexafluoroantimonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, tetraphenylphosphonium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluoroantimonate, tris [4- (dibutylamino) phenyl ] ammonium hexafluoroantimonate, 4-octyloxybis (diphenyliodonium hexafluoroantimonate), bis (4-dodecylbenzene) iodonium hexafluoroantimonate, N-ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-ethylpyridinium hexafluorophosphate, 1-hexyl-3-methylpyridinium hexafluorophosphate, 1-ethyl-3-methylimidazoline trifluoro (trifluoromethyl) borate, 1-butyl-3-methylimidazoline dibutyl phosphate, 1-butylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, trimethyloxonium hexachloroantimonate triphenyl carbon pentachloronitine stannic acid.
10. The method for preparing a colored carbon fiber material based on electropolymerization technique according to claim 1, wherein: the mass of the initiator added in the step (2) is 0.05-5% of the mass of the monomer.
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US4272346A (en) * | 1979-12-03 | 1981-06-09 | Washington State University Research Foundation | Treatment of carbon fibers to decrease electrical hazards of conductive fiber fragment release |
CN109881197A (en) * | 2019-04-16 | 2019-06-14 | 安庆北化大科技园有限公司 | A method of based on electropolymerization technology in metal material surface coating |
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