CN117569076A - Preparation method of aramid fiber for electromagnetic shielding - Google Patents
Preparation method of aramid fiber for electromagnetic shielding Download PDFInfo
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- CN117569076A CN117569076A CN202311481643.8A CN202311481643A CN117569076A CN 117569076 A CN117569076 A CN 117569076A CN 202311481643 A CN202311481643 A CN 202311481643A CN 117569076 A CN117569076 A CN 117569076A
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- electromagnetic shielding
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 238000007772 electroless plating Methods 0.000 claims abstract description 11
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 9
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 37
- 239000004760 aramid Substances 0.000 claims description 18
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 238000007747 plating Methods 0.000 description 13
- 101710134784 Agnoprotein Proteins 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- -1 pyridine diamine Chemical class 0.000 description 10
- 229920003235 aromatic polyamide Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—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
- D06M15/59—Polyamides; Polyimides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a preparation method of aramid fiber for electromagnetic shielding. The method comprises the following steps: an ultrathin crosslinked layer containing active carboxyl, pyridine or imidazole units is constructed on the surface of commercial meta-aramid fiber through interfacial polymerization reaction, simultaneously, metal ions such as Cu < 2+ >, ag < + >, ni < 2+ > and the like are synchronously introduced into a reaction solution through coordination action of active groups and metal ions, metal nano particles are formed on the surface of the aramid fiber after in-situ reduction to serve as seed crystals, and then a thin and uniform continuous metal conductive coating is efficiently constructed on the surface of the aramid fiber through metal electroless plating; the ultrathin crosslinked layer does not influence the excellent flexibility of the aramid fiber and does not damage the mechanical property of the aramid fiber, and the strong interface composition of the metal particles and the fiber can be realized based on the coordination effect of the active groups of the ultrathin crosslinked layer and the metal ions, so that the adhesive force of the metal conductive layer on the fiber surface is improved.
Description
Technical Field
The invention belongs to the technical field of high-performance fiber preparation, and particularly relates to a preparation method of high-performance aramid fiber capable of meeting electromagnetic shielding application.
Background
As one of high-performance organic fibers, the aramid fiber has the excellent characteristics of high strength, high modulus, excellent heat resistance, intrinsic flame retardance, corrosion resistance and the like, and is widely applied to the fields of aerospace, army equipment, information communication, transportation and the like. Conductive aramid fibers prepared by constructing a continuous conductive coating on the surface of the aramid fibers through chemical or physical modification are currently attracting attention in the electromagnetic shielding field. However, the surface of the aramid fiber is smooth, has strong chemical inertia, is difficult to be combined with other materials, and cannot obtain a continuous and stable metal layer on the surface by physical sputtering, conventional chemical plating deposition and other methods, so that the surface modification treatment of the aramid fiber to improve the reactivity of the aramid fiber is a key to obtaining the high-performance conductive aramid fiber fabric.
In order to improve the binding force of the aramid fiber and the conductive coating, the prior treatment measures for the surface of the aramid fiber mainly comprise plasma etching, acid-base etching, chemical grafting and the like. Taking acid-base etching as an example, the main process flow comprises the steps of etching the surface of the fiber by using strong acid or alkali liquor to form a rough groove structure or damage an amide unit on the surface to form an active carboxyl, forming active points of metal nano particles on the surface of the fiber by mechanical engagement or ion coordination, and forming a metal conductive coating on the surface of the fiber by metal chemical plating. For example, the national patent of the application number CN202010242357.6 discloses a method for preparing conductive aramid paper by cleaning aramid and then improving an aramid and metal silver coating by a plasma etching method, and the national patent of the application number CN201911326096.X discloses a method for preparing aramid with a composite metal coating structure, which also comprises the core process of pretreating fibers by using sulfuric acid solution and dimethyl sulfoxide (DMSO) solution of calcium chloride, improving the surface activity and realizing efficient compounding of metal and fibers. The national patent of the invention with the application number of CN201310685423.7 discloses a method for preparing conductive aramid fibers by firstly roughening the surface of the aramid fibers by NaOH etching treatment, then activating by palladium metal and chemically plating silver. However, both physical and chemical etching always results in a decrease in the mechanical properties of the fibers at the expense of compromising the physical morphology or chemical structure of the fibers; in addition, the formation of the metal nanoparticle 'seed' and the pretreatment of the fiber in the process flow are independent and separated, and the process flow is complicated.
The lone pair electrons on oxygen or nitrogen atoms in common organic functional groups (such as carboxyl, imidazole, pyridine, 1,2, 4-triazole and the like) have stronger coordination ability with metal ions (Macromolecular Rapid Communications,2022,43 (3): 2100643; polymers,2020,12 (2): 442), and the strong interface recombination of the polymer and the metal nano particles can be realized by utilizing the special interaction. However, how to realize the construction of such special interactions on the surface of aramid fibers without damaging the inherent mechanical properties and flexibility of the aramid fibers, so that the efficient construction of continuous metal conductive coatings is still an important challenge in the field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of conductive aramid fiber for electromagnetic shielding, which aims to overcome the problems of damage to the mechanical properties of fibers caused by physical or chemical etching action and low efficiency caused by complex process flow in the prior art.
The invention provides a preparation method of aramid fiber for electromagnetic shielding, which mainly comprises the steps of immersing meta-aramid fiber in a mixed solution of diamine monomer/ethanol/metal salt containing active carboxyl, pyridine or imidazole units for a period of time, transferring the meta-aramid fiber into trimesoyl chloride (TMC)/normal hexane solution, and keeping the meta-aramid fiber at room temperature for a period of time; treating the obtained aramid fibers with a reducing agent to form metal nano particles on the surfaces of the fibers, and then carrying out metal electroless plating on the fibers to construct a continuous metal conductive layer on the surfaces; finally, washing and drying the aramid fiber by deionized water to prepare the aramid fiber for electromagnetic shielding.
The diamine containing active carboxyl, pyridine or imidazole units has a chemical structure as follows:
the metal salt is one of copper chloride, silver nitrate, nickel nitrate or nickel sulfate.
The composition of the diamine monomer/ethanol/metal salt mixed solution containing active carboxyl, pyridine or imidazole units is as follows by mass percent: (3-5) wt%: (90-92 wt%): (3-7 wt%) and the treatment time of the aramid fiber in the mixed solution of diamine monomer containing active carboxyl, pyridine or imidazole unit and ethyl alcohol/metal salt is (10-15) min, at room temperature.
The concentration of the TMC/n-hexane solution is (10-25) mmol/L, the treatment time of the aramid fiber in the solution is (1-3) min, and the room temperature is reached.
The reducing agent is sodium borohydride NaBH 4 Hypophosphorous acid H 3 PO 2 Or sodium hypophosphite NaH 2 PO 2 One of the aqueous solutions, and the concentration of the reducing agent is (0.1-0.5) mol/L.
The chemical plating solution is commercial chemical plating solution containing silver, copper and nickel metal salts.
According to the invention, the trimesoyl chloride and the diamine monomer containing active groups are subjected to interfacial polymerization reaction on the surface of the aramid fiber to form an ultrathin crosslinked layer, so that the surface activity of the aramid fiber is improved, and a metal coordination effect is synchronously formed, thereby anchoring the metal nano particles; meanwhile, the formed ultrathin crosslinked layer is favorable for protecting the aramid fiber from being corroded by chemical reagents in the subsequent metal electroless plating process, so that the mechanical property is attenuated. The invention can efficiently and continuously prepare the conductive aramid fiber and meet the application requirements of the current electromagnetic shielding.
Advantageous effects
(1) The invention builds an ultrathin crosslinked layer on the surface of the aramid fiber through diamine and trimesoyl chloride, so that the excellent flexibility of the aramid fiber is not affected, the mechanical property of the aramid fiber is not damaged, and the invention is a nondestructive surface modification method;
(2) The coordination effect of the active groups and metal ions based on the ultrathin crosslinked layer can realize the strong interface compounding of metal particles and fibers, promote the adhesive force of the metal conductive layer on the surfaces of the fibers, and have more outstanding conductive stability in severe environments such as repeated bending, chemical corrosion and the like;
(3) The ultrathin crosslinked layer and the metal coordination function are formed synchronously, so that the preparation process flow is simplified, and the large-scale development is facilitated;
(4) The formation of the ultrathin crosslinked layer on the surface of the aramid fiber can fully protect the aramid fiber from being corroded by chemical reagents in subsequent metal plating solutions.
Drawings
Fig. 1 is an SEM photograph of an unmodified aramid surface in the present invention, fig. 2 is an SEM photograph of an aramid surface of a conductive layer containing metallic silver in example 1, fig. 3 is an EDS photograph of an element silver on an aramid surface of a conductive layer containing metallic silver in example 1, and fig. 4 is a change in resistance of an aramid fabric containing metallic silver conductive layer in example 1 after ultrasonic cleaning in different solvents.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The sources of the fiber materials, sample processing and testing conditions in the examples of the present invention:
meta-aramid is purchased from Takappan New Material application Co., ltd, and the specification is 200D;
carboxydiamines: purchased from zheng state convergence chemical company, inc;
pyridine diamine: purchased from Shanghai ziao chemical technology Co., ltd;
imidazole diamine: purchased from Changzhou sunlight pharmaceutical Co., ltd;
nickel nitrate: purchased from Shanghai Ala Biochemical technologies Co., ltd.
And (3) fiber bending treatment: repeatedly bending the fiber containing the metal coating by self-made equipment for 1000 times;
corrosion resistance test of fibers: treatment of the metal-coated fibers with water, HCl (0.1 mol/L), naOH (0.1 mol/L), sodium chloride (0.1 mol/L) and acetone solution;
mechanical properties: the tensile rate is 5cm/min and the clamp distance is 2cm by adopting an Instron3300 test;
fiber resistance test: the resistance of the fiber was measured at room temperature using a Kaisi DT-9205A high precision resistance multimeter with a control length of 20cm, and 10 sets of data were measured for each sample, and averaged.
Example 1
Taking a proper amount of commercial meta-aramid fiber, directly immersing the commercial meta-aramid fiber in carboxyl diamine monomer/ethanol/AgNO without pretreatment 3 In the mixed solution, carboxyl diamine, ethanol and AgNO 3 The mass fractions of (2) are respectively 4%:90% >: 6% at room temperature15min. Then the aramid fiber treated by the diamine is immersed in TMC/normal hexane solution, wherein the concentration of TMC is 20mol/L, and the treatment time is 3min. The treated fiber is taken out and immersed in sodium borohydride NaBH 4 Treating the fiber in a solution at 40deg.C for 2min, and continuously passing the fiber through a commercial electroless plating solution (3.5 g AgNO 3 5mL of ammonia water, 60mL of water) and a reducing solution (45 g of glucose, 4g of tartaric acid, 10mL of ethanol and 1L of water), and the electroless metal plating time was controlled to 2min. Finally, the fiber is washed by deionized water and dried at 60 ℃ to obtain the aramid fiber with the surface plated with the silver conductive layer.
Example 2
Taking a proper amount of commercial meta-aramid fiber, directly immersing the meta-aramid fiber in pyridine diamine-II monomer/ethanol/AgNO without pretreatment 3 In the mixed solution, carboxyl diamine, ethanol and AgNO 3 The mass fractions of (2) are respectively 4%:90% >: 6, hold at room temperature for 15min. Then the aramid fiber treated by the diamine is immersed in TMC/normal hexane solution, wherein the concentration of TMC is 20mol/L, and the treatment time is 3min. The treated fiber is taken out and immersed in sodium borohydride NaBH 4 Treating the fiber in a solution at 40deg.C for 2min, and continuously passing the fiber through a commercial electroless plating solution (3.5 g AgNO 3 5mL of ammonia water, 60mL of water) and a reducing solution (45 g of glucose, 4g of tartaric acid, 10mL of ethanol and 1L of water), and the electroless metal plating time was controlled to 2min. Finally, the fiber is washed by deionized water and dried at 60 ℃ to obtain the aramid fiber with the surface plated with the silver conductive layer.
Example 3
Taking a proper amount of commercial meta-aramid fiber, directly immersing the commercial meta-aramid fiber in imidazole diamine-1/ethanol/CuCl without pretreatment 2 In the mixed solution, carboxyl diamine, ethanol and CuCl 2 The mass fractions of (2) are respectively 5%:90% >: 5%, hold at room temperature for 15min. Then the aramid fiber treated by the diamine is immersed in TMC/normal hexane solution, wherein the concentration of TMC is 22mol/L, and the treatment time is 3min. The treated fiber is taken out and immersed in sodium borohydride NaBH 4 Treating in solution for 2min at 40deg.C, and dissolving fiber in commercially available copper saltElectroless plating solution (10 g of copper chloride, 2g N-methylmorpholine, 4g of formaldehyde, 13g of sodium hydroxide, 10g of sodium tartrate, 20g of EDTA-2 Na,0.1g of potassium ferrocyanide, 0.01g of bipyridine, 50mL of methanol, 1L of water) was prepared, and the electroless metal plating time was controlled to 2min. Finally, the fiber is washed by deionized water and dried at 60 ℃ to obtain the aramid fiber with the surface plated with the copper conductive layer.
Example 4
Taking a proper amount of commercial meta-aramid fiber, directly immersing the meta-aramid fiber in imidazole diamine-I/ethanol/Ni (NO) 3 ) 2 In the mixed solution, carboxyl diamine, ethanol and AgNO 3 The mass fractions of (2) are respectively 5%:90% >: 5%, hold at room temperature for 15min. Then the aramid fiber treated by the diamine is immersed in TMC/normal hexane solution, wherein the concentration of TMC is 25mol/L, and the treatment time is 3min. The treated fiber is taken out and immersed in sodium borohydride H 3 PO 2 Treating in solution for 5min at 40deg.C, and continuously passing the fiber through electroless plating solution (NiCl) containing metallic nickel salt solution 2 ·6H 2 O:20g/L，NaH 2 PO 2 ·H 2 O:30g/L，Na 3 C 6 H 5 O 7 ·2H 2 O:10g/L，NH 4 Cl 30g/L, pH=8.5-9.5) and controlling the electroless metal plating time to be 3min. Finally, the fiber is washed by deionized water and dried at 60 ℃ to obtain the aramid fiber with the surface plated with the silver conductive layer.
Comparative example 1
Taking a proper amount of commercial meta-aramid fiber, coarsening and pre-treating the aramid fiber by using NaOH solution (200 g of NaOH,50g of absolute ethyl alcohol and 950mL of water) according to the method reported in application number CN201310685423.7, and immersing the aramid fiber in AgNO 3 In ethanol solution (6 wt%) for 15min at room temperature. The treated fiber is taken out and immersed in sodium borohydride NaBH 4 Treating the fiber in a solution at 40deg.C for 2min, and continuously passing the fiber through a commercial electroless plating solution (3.5 g AgNO 3 5mL of ammonia water, 60mL of water) and a reducing solution (45 g of glucose, 4g of tartaric acid, 10mL of ethanol and 1L of water), and the electroless metal plating time was controlled to 2min. Finally, the fiber is washed by deionized waterAnd drying at 60 ℃ to obtain the aramid fiber with the surface plated with the silver conductive layer.
Comparative example 2
Taking a proper amount of commercial meta-aramid fiber, directly immersing the commercial meta-aramid fiber in carboxyl diamine monomer/ethanol/AgNO without pretreatment 3 In the mixed solution, carboxyl diamine, ethanol and AgNO 3 The mass fractions of (2) are respectively 4%:90% >: 6, hold at room temperature for 15min. Then the aramid fiber treated by the diamine is immersed in terephthaloyl chloride/normal hexane solution, wherein the concentration of TMC is 20mol/L, and the treatment time is 3min, at this time, a linear molecular chain polymer film rather than a crosslinked film is formed on the surface of the aramid fiber. The treated fiber is taken out and immersed in sodium borohydride NaBH 4 Treating the fiber in a solution at 40deg.C for 2min, and continuously passing the fiber through a commercial electroless plating solution (3.5 g AgNO 3 5mL of ammonia water, 60mL of water) and a reducing solution (45 g of glucose, 4g of tartaric acid, 10mL of ethanol and 1L of water), and the electroless metal plating time was controlled to 2min. Finally, the fiber is washed by deionized water and dried at 60 ℃ to obtain the aramid fiber with the surface plated with the silver conductive layer.
Table 1 shows the comparison of the electrical conductivity and mechanical properties of the modified aramid fibers prepared by the present invention and those reported in the invention patent CN202010242357.6, CN202110126531.5 and research literature Adv.Eng.Mater.2019,21,1801041 (literature 1)).
TABLE 1
As can be seen from comparative example 1, the process adopts strong alkali NaOH to pretreat the surface of the aramid fiber, and forms active sites on the surface of the aramid fiber, which is favorable for complexing metal silver ions, but from the end effect, on one hand, the strong alkali treatment seriously damages the mechanical property of the fiber, and on the other hand, the electromagnetic shielding effectiveness of the prepared fabric is still lower than that of the patent of the invention.
As can be seen from comparative example 2, the use of terephthaloyl chloride instead of TMC resulted in the formation of a linear polymer film on the surface of aramid fiber, which had a higher resistance change rate after 1000 times of bending than the present invention, and the structure of the surface conductive metal layer was unstable.
Claims (7)
1. A preparation method of aramid fiber for electromagnetic shielding is characterized in that meta-aramid fiber is immersed in a mixed solution of diamine monomer containing active carboxyl, pyridine or imidazole units, ethanol and metal salt for a period of time, and then transferred into trimesoyl chloride (TMC)/normal hexane solution for a period of time at room temperature; treating the obtained aramid fibers with a reducing agent to form metal nano particles on the surfaces of the fibers, and then carrying out metal electroless plating on the fibers to construct a continuous metal conductive layer on the surfaces;
finally, washing and drying the aramid fiber by deionized water to prepare the aramid fiber for electromagnetic shielding.
2. The method for producing an aramid fiber for electromagnetic shielding according to claim 1, wherein the diamine containing an active carboxyl group, pyridine or imidazole unit has a chemical structure of one of the following:
3. the method for producing aramid fiber for electromagnetic shielding according to claim 1, wherein the metal salt is one of copper chloride, silver nitrate, nickel nitrate or nickel sulfate.
4. The method for producing an aramid fiber for electromagnetic shielding according to claim 1, wherein the composition of the mixed solution of diamine monomer/ethanol/metal salt containing active carboxyl group, pyridine or imidazole unit is as follows by mass: (3-5) wt%: (90-92 wt%): (3-7 wt%) and the treatment time of the aramid fiber in the mixed solution of diamine monomer containing active carboxyl, pyridine or imidazole unit and ethyl alcohol/metal salt is (10-15) min, at room temperature.
5. The method for producing an aramid fiber for electromagnetic shielding according to claim 1, wherein the concentration of TMC/n-hexane solution is (10-25) mmol/L, and the treatment time of the aramid fiber in the solution is (1-3) min at room temperature.
6. The method for preparing aramid fiber for electromagnetic shielding according to claim 1, wherein the reducing agent is sodium borohydride NaBH 4 Hypophosphorous acid H 3 PO 2 Or sodium hypophosphite NaH 2 PO 2 One of the aqueous solutions, and the concentration of the reducing agent is (0.1-0.5) mol/L.
7. The method for producing aramid fiber for electromagnetic shielding according to claim 1, wherein the electroless plating solution is commercially available electroless plating solution containing silver, copper, nickel metal salts.
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