CN112477352B - 一种石墨烯导电面料 - Google Patents
一种石墨烯导电面料 Download PDFInfo
- Publication number
- CN112477352B CN112477352B CN202011100148.4A CN202011100148A CN112477352B CN 112477352 B CN112477352 B CN 112477352B CN 202011100148 A CN202011100148 A CN 202011100148A CN 112477352 B CN112477352 B CN 112477352B
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- CN
- China
- Prior art keywords
- fabric
- agent
- coating
- graphene
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004744 fabric Substances 0.000 title claims abstract description 122
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 57
- 238000000576 coating method Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 229920000767 polyaniline Polymers 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 229920006264 polyurethane film Polymers 0.000 claims abstract description 28
- 239000011247 coating layer Substances 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 238000007731 hot pressing Methods 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims abstract description 15
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000010030 laminating Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000839 emulsion Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000002759 woven fabric Substances 0.000 claims description 5
- 230000035699 permeability Effects 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229920004933 Terylene® Polymers 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000002940 repellent Effects 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
- B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/14—Mixture of at least two fibres made of different materials
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- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
本发明公开了一种石墨烯导电面料，包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层，所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、粘合剂、增稠剂和水组成的涂层剂形成。制备面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，烘干、焙烘形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜。先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压时间和热压温度，待温度达到后，进行压烫，完成热压复膜。本发明采用在基材面料一面设置导电涂层、另一面复导电膜的方法，实现了面料的防水、透湿、导电的功能。
Description
技术领域
本发明属于功能纺织品面料领域，具体涉及含石墨烯及薄膜复合导电面料。
背景技术
纺织品在使用过程中,易因摩擦和感应产生静电，不仅影响外观和舒适性,还对人体健康有害。因此，无论日常服用织物，或是电子信息、制药、石油、化工等工业生产中工人的防护服都需要一定的抗静电性能，以防止对人体健康损害和危险事故的发生。在这样的大环境下，抗静电织物的研发显得尤为重要，即赋予织物导电性使得静电消除。同时，由于石油、化工等行业的工人长时间在比较恶劣的环境下工作，其工作服往往需要一定的防水透湿性能，保证工人长时间穿着舒适性。因此，在织物抗静电的基础上，也有必要赋予织物一定的防水透湿性能。如何制造出兼具抗静电性能和防水透湿性能的功能性面料成为各个纺织企业的研究热点。
目前，导电织物的制备方法主要有两类：导电纤维和涂层法制备导电织物。
第一类是将导电纤维直接编织成导电织物，赋予织物良好的导电性能。导电纤维又分金属纤维，碳纤维和高聚物导电纤维这几类。
(1)金属纤维具有优良的导电性，但它的耐磨性、耐曲折性较差，与其它服用纤维混合性差，在一定程度上限制了它的加工方法和用途。
(2)碳纤维的导电性能良好，耐热、耐化学药品，密度小、强度高、热导性好，但缺乏韧性，不耐弯折，无热收缩能力，不适于纺织品使用。此外，碳材料均为黑色，复合纺丝制得的导电纤维为灰黑色，其在使用上受到了一定的限制。
(3)导电高聚物不仅具有特别的电学性能和光学性能，而且还兼备高聚物的加工性和柔韧性、无机材料的半导体性和金属的导电性，因此近年来成为研究的热点。但是目前制备这样的导电织物时，对于织物的选择、氧化剂的选择和用量、掺杂剂的选择和用量以及加工方法的选择等工艺条件尚未成熟，并且要求导电高聚物与纤维具有较好的亲和力，因此这样的导电织物还处于理论研究阶段，难以大规模生产应用。
涂层导电织物是将导电涂料涂覆到织物上，赋予织物良好的导电性能。与导电纤维工艺复杂，难以控制相比，涂层法的工艺条件简单易控制，导电涂料选择具有多样性，因此涂层导电织物是各企业研发的热点。导电涂料主要由三部分组成：作为粘结剂的成膜基体材料，具有一定导电性能的填料粒子以及改善涂料应用性能的助剂。其中具有导电性的填料粒子是决定涂层织物导电性能的关键，因此导电性填料粒子的选择至关重要。目前常用的导电材料主要有：碳材料、高分子导电聚合物、金属及其金属氧化物。
碳材料的特点是具有较大的比表面积、良好的导电性以及化学惰性。比表面积较大的碳材料可以提供更广阔的电子迁移通路，从而具备优良的导电性能。目前研究较多的碳材料包括石墨烯、活性炭、碳纳米管等。其中石墨烯以其各方面优异的性能，被人们广泛关注。
高分子导电聚合物其实是一种半导体，其本身并不导电，但是在质子酸掺杂后，可以通过在分子链中发生快速可逆的掺杂/脱掺杂过程，进行电荷转移从而变为导电材料。目前研究较多的高分子导电聚合物主要有聚苯胺，聚吡咯和聚噻吩等，而聚苯胺(PANI)因其物美价廉，从高分子导电聚合物中脱颖而出。
金属材料一直以来都具有良好的导电性能，常见的铜、银、铝等金属电阻率(Ω·m)可达10-8的数量级，导电性能相当优异。但是这些金属材料价格昂贵，不适合应用于低成本、大批量生产的纺织行业。
综上所述，导电织物目前适合采用涂层法制备，而石墨烯和聚苯胺以其优异的导电性可以作为涂层中导电填料的选择对象。
发明内容
本发明目的是提供一种石墨烯导电面料及其制备方法，通过在面料表面复膜、涂层的方法实现。具体来说，本发明先将含聚苯胺接枝石墨烯复合材料的导电涂层剂以单面涂覆工艺施加到基材面料表面上，形成石墨烯涂覆层，再在基材面料涂层另一面复合石墨烯导电膜，形成具有良好导电、防水透湿性能的功能面料。
一种石墨烯导电面料，包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层，所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、粘合剂、增稠剂和水组成的涂层剂形成；
所述的防水剂，制备方法为：
1)乳化剂十二烷基硫酸钠、OS-15、TX-30以及去离子水于乳化釜中，搅拌、溶解，形成乳化剂溶液；另取BA、MMA、St及正十六烷搅拌混匀成混合单体；将混合单体加入乳化剂溶液中，搅拌乳化30min，超声处理15min，得乳化液；
2)在装有电动搅拌器、恒压滴液漏斗、回流冷凝管的反应器中加入十二烷基硫酸钠、乳化剂OS-15、去离子水，搅拌溶解，加入经表面改性的纳米SiO2，分散均匀，升温加热至78℃时，加入1/2体积乳化液及1/3体积引发剂水溶液，待反应温度稳定，乳液呈明显蓝光后，保温反应30min，然后升温至82℃，滴加剩余乳化液和1/3体积引发剂水溶液，2h内滴完；
3)滴加正十六烷和MMA、BA及如式1所示的有机硅单体混合液，滴加时间为1h左右，补加1/3体积引发剂水溶液，加料完毕后，升温到86℃，保温45min，停止加热，当反应体系温度降为40℃以下时出料，得防水剂乳液。
所述的基材面料为针织面料或梭织面料。
所述的薄膜为含石墨烯粉末的聚氨酯薄膜。
制备石墨烯导电面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜，具体步骤如下：
1)、配置涂层剂；
2)、涂层：基材面料表面涂覆涂层剂、烘干、焙烘；
3)、复膜：先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压时间和热压温度，待温度达到后，进行压烫，完成热压复膜。
所述的配置涂层剂步骤，具体为：在水中加入分散剂，搅拌均匀，缓慢加入聚苯胺接枝石墨烯复合材料，搅拌均匀后，超声分散30-60分钟，制备得到稳定的聚苯胺接枝石墨烯复合材料分散液，然后在搅拌下将防水剂、粘合剂乳液缓慢加入聚苯胺接枝石墨烯复合材料分散液中，搅拌均匀，最后以增稠剂调节粘度，即制得石墨烯涂层剂。
本发明有益效果：
层压织物的核心部分为防水透湿膜，目前市售的防水透湿功能膜主要为聚四氟乙烯疏水微孔膜和聚氨酯亲水无孔膜。这些膜虽然具有优异的防水透湿性能，但是无法满足石油、化工等行业对服装导电性的要求。
本发明采用在基材面料一面设置导电涂层、另一面复导电膜的方法，实现了面料的防水、透湿、导电的功能。
1)、防水剂兼容到复合材料的涂层液中，赋予面料良好的防水性能。
2)、面料具有良好的导电性能，表面电阻率小于105Ω，面料导电性能耐久性良好。
3)、面料的耐静水压达到10000毫米水柱、透湿性达10000g/(m2·24h)以上，具有优异的防水透湿性能。
具体实施方式
以下通过具体实施方式对本发明作进一步说明。如无特殊说明，本发明涉及的原料质量单位“份”为质量份。
本发明公开了一种石墨烯导电面料，通过在基材面料的两侧分别涂覆涂层剂、复膜形成。具体来说，本发明石墨烯导电面料包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层。
其中，
所述的基材面料为针织面料或梭织面料，优选的，针织面料可以为30D/24F40针，90％涤纶、10％氨纶、梭织面料可以为75D+40D*75D+40D/150D+40D，100％涤纶。
所述薄膜层，采用的薄膜为含石墨烯粉末的聚氨酯薄膜，厚度为0.02-0.08mm。
所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂、水和粘合剂组成的涂层剂形成，其中聚苯胺接枝石墨烯复合材料、防水剂的添加量根据导电、防水性能的需求而定；分散剂为聚丙烯酸钠，主要作用是分散石墨烯复合材料；粘合剂采用市售聚丙烯酸酯乳液，为成膜组分；增稠剂为聚丙烯酸，调节涂层剂体系的粘度6000-8000mPa·s。
石墨烯涂覆层中，所述的聚苯胺接枝石墨烯复合材料，制备方法为：将20mg氨基化石墨烯粉末加入到40mL盐酸溶液中(1mol/L)，超声分散30min得分散液，将分散液放置在水浴中冷却至一定的温度，然后加入一定量的苯胺单体搅拌一段时间，称取一定比例的过硫酸铵并配成0.5mol/L的过硫酸铵溶液，缓慢滴加过硫酸铵溶液至混合液中，几分钟后黑色分散液变绿，说明苯胺接枝聚合反应开始，保持水浴搅拌状态，反应一段时间，反应结束后，先将产物用1mol/L的盐酸溶液清洗过滤，再用丙酮和去离子水离心洗涤3次，最后置于冷冻干燥机中干燥后即得聚苯胺接枝石墨烯的复合材料。
氨基化石墨烯粉末，粒径：0.5-4.0μm、N含量：2.4-6.2wt％。
石墨烯涂覆层中，所述的防水剂，制备方法为：
1)乳化剂十二烷基硫酸钠、OS-15、TX-30以及去离子水于乳化釜中，搅拌、溶解，形成乳化剂溶液；另取BA、MMA、St及正十六烷搅拌混匀成混合单体；将混合单体加入乳化剂溶液中，搅拌乳化30min，超声处理15min，得乳化液；
2)在装有电动搅拌器、恒压滴液漏斗、回流冷凝管的反应器中加入十二烷基硫酸钠、乳化剂OS-15、去离子水，搅拌溶解，加入经表面改性的纳米SiO2，分散均匀，升温加热至78℃时，加入1/2体积乳化液及1/3体积引发剂水溶液，待反应温度稳定，乳液呈明显蓝光后，保温反应30min，然后升温至82℃，滴加剩余乳化液和1/3体积引发剂水溶液，2h内滴完；
3)滴加正十六烷和MMA、BA及如式1所示的有机硅单体混合液，滴加时间为1h左右，补加1/3体积引发剂水溶液，加料完毕后，升温到86℃，保温45min，停止加热，当反应体系温度降为40℃以下时出料，得防水剂乳液。
其中，所述的表面改性的纳米SiO2，制备方法为：
取20份硅烷偶联剂乙烯基三乙氧基硅烷于烧杯中并加20份水于烧杯中，用0.1mol/L的盐酸调pH值到3-4，磁力搅拌水解1h，形成偶联剂水解溶液；往接有冷凝管的反应器中，加入10份干燥后的纳米SiO2，50份无水乙醇溶剂，设置反应温度为70℃，在反应釜中磁力搅拌30分钟，再滴入20份的水解后的偶联剂溶液反应3h，制得表面改性纳米SiO2。
制备石墨烯导电面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜，具体步骤如下：
1)、配置涂层剂；
2)、涂层：基材面料表面涂覆涂层剂、烘干、焙烘；
3)、复膜：先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压时间和热压温度，待温度达到后，进行压烫，完成热压复膜，制成所述的石墨烯导电面料。
所述的配置涂层剂步骤，具体为：在水中加入分散剂，搅拌均匀，缓慢加入聚苯胺接枝石墨烯复合材料，搅拌均匀后，超声分散30-60分钟，制备得到稳定的聚苯胺接枝石墨烯复合材料分散液，然后在搅拌下将防水剂、粘合剂乳液缓慢加入聚苯胺接枝石墨烯复合材料分散液中，搅拌均匀，最后以增稠剂调节粘度，即制得石墨烯涂层剂。
实施例1：
本发明所述防水剂乳液制备方法为：
(1)纳米SiO2表面改性
取20份硅烷偶联剂乙烯基三乙氧基硅烷于烧杯中并加20份水于烧杯中，用0.1mol/L的盐酸调pH值到3-4，磁力搅拌水解1h，形成偶联剂水解溶液；往接有冷凝管的反应器中，加入10份干燥后的纳米SiO2，50份无水乙醇溶剂，设置反应温度为70℃，在反应釜中磁力搅拌30分钟，再滴入20份水解后的偶联剂溶液，反应3h，制得表面改性纳米SiO2；
(2)防水剂乳液合成
1)乳化剂十二烷基硫酸钠2.5份、OS-15 2份、TX-30 4份以及去离子水100份置于乳化釜中，搅拌、溶解，形成乳化剂溶液；另取丙烯酸丁酯(BA)42份、甲基丙烯酸甲酯(MMA)9份、苯乙烯(St)6份及正十六烷2份搅拌混匀成混合单体；将混合单体加入乳化剂溶液中，搅拌乳化30min，超声处理15min，得乳化液；
2)在装有电动搅拌器、恒压滴液漏斗、回流冷凝管的反应器中加入2份十二烷基硫酸钠、1.6份OS-15、3.2份TX-30、80份去离子水，搅拌溶解；加入16份经表面改性的纳米SiO2，分散均匀，升温加热至78℃时，加入1/2体积的乳化液及1/3体积的引发剂水溶液，待反应温度稳定，乳液呈明显蓝光后，保温反应30min，然后升温至82℃，滴加剩余乳化液和1/3体积的引发剂水溶液，2h内滴完；
3)滴加3份正十六烷和6份甲基丙烯酸甲酯(MMA)、14份丙烯酸丁酯(BA)及9份如式1所示有机硅单体的混合液，滴加时间为1h左右，补加剩余1/3体积的引发剂水溶液，加料完毕后，升温到86℃，保温45min，停止加热，当反应体系温度降为40℃以下时出料，得防水剂乳液。所述的引发剂水溶液由0.24份过硫酸钠溶于30份水中形成。
所述的有机硅单体，由2-(三甲基硅氧基)乙醇胺与甲基丙烯酸异氰酸酯乙酯反应制成，其方法如下：
在装有搅拌器、温度计、冷凝管的反应器中，加入经脱水处理的2-(三甲基硅氧基)乙醇胺、甲基丙烯酸异氰酸酯乙酯、二月桂酸二丁基锡，100℃搅拌反应5h，得含C＝C键的功能性有机硅单体；2-(三甲基硅氧基)乙醇胺、甲基丙烯酸异氰酸酯乙酯的摩尔比1:1，二月桂酸二丁基锡的质量占反应单体总质量的0.4％。
应用例1：
取实施例1制得的防水剂乳液100份，以增稠剂聚丙烯酸调节粘度6000-8000mPa·s，以160-200g/m2量在75D+40D*75D+40D/150D+40D涤纶面料表面涂层，于100℃预烘2min、180℃焙烘1min，制成防水涂层面料。
防水涂层面料防泼水(洗前)100分、5次水洗后80分，涂层表面静态接触角达130°。
实施例2：
一种石墨烯导电面料，包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层，所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂和粘合剂组成的涂层剂形成；
所述的基材面料为针织面料，规格为30D/24F 40针，90％涤纶、10％氨纶。
所述薄膜层，采用的薄膜为含石墨烯粉末的聚氨酯薄膜，厚度为0.06mm。
石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂和粘合剂组成的涂层剂形成，其中聚苯胺接枝石墨烯复合材料、分散剂、防水剂和粘合剂质量比4:0.5:32:57、增稠剂调节粘度6000-8000mPa·s。防水剂按实施例1方法制备。
制备石墨烯导电面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜，具体步骤如下：
1)、配置涂层剂：在水中加入聚丙烯酸钠，搅拌均匀至完全溶解，缓慢加入聚苯胺接枝石墨烯复合材料，搅拌均匀后，超声分散30-60分钟，制备得到稳定的聚苯胺接枝石墨烯复合材料分散液，然后在搅拌下将防水剂、聚丙烯酸酯乳液缓慢加入聚苯胺接枝石墨烯复合材料分散液中，搅拌均匀，最后以增稠剂调节粘度6000-8000mPa·s，即制得石墨烯涂层剂；
2)、涂层：基材面料表面涂覆涂层剂160g/m2，100℃、2min烘干，160℃、30s焙烘；
3)、复膜：先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压温度105℃和热压时间30s，待温度达到后，进行压烫，完成热压复膜，制成所述的石墨烯导电面料。
石墨烯导电面料的性能：耐静水压11000mmH2O，透湿性10000g/m2·24h，剥离强度达5N/cm，表面电阻率5×104Ω，防泼水(洗前)100分。
实施例3：
一种石墨烯导电面料，包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层，所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂和粘合剂组成的涂层剂形成；
所述的基材面料为梭织面料，规格为75D+40D*75D+40D/150D+40D涤纶面料，100％涤纶。
所述薄膜层，采用的薄膜为含石墨烯粉末的聚氨酯薄膜，厚度为0.03mm。
石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂和粘合剂组成的涂层剂形成，其中聚苯胺接枝石墨烯复合材料、分散剂、防水剂和粘合剂质量比3:0.3:28:45、增稠剂调节粘度6000-8000mPa·s。防水剂按实施例1方法制备。
制备石墨烯导电面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜，具体步骤如下：
1)、配置涂层剂：在水中加入聚丙烯酸钠，搅拌均匀至完全溶解，缓慢加入聚苯胺接枝石墨烯复合材料，搅拌均匀后，超声分散30-60分钟，制备得到稳定的聚苯胺接枝石墨烯复合材料分散液，然后在搅拌下将防水剂、聚丙烯酸酯乳液缓慢加入聚苯胺接枝石墨烯复合材料分散液中，搅拌均匀，最后以增稠剂调节粘度6000-8000mPa·s，即制得石墨烯涂层剂；
2)、涂层：基材面料表面涂覆涂层剂140g/m2，100℃、2min烘干，160℃、30s焙烘；
3)、复膜：先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压温度110℃和热压时间24s，待温度达到后，进行压烫，完成热压复膜，制成所述的石墨烯导电面料。
石墨烯导电面料的性能：耐静水压10000mmH2O，透湿性12000g/m2·24h，剥离强度达4N/cm，表面电阻率8×104Ω，防泼水(洗前)100分。
防泼水性能测试方法参照AATCC22。
Claims (6)
1.一种石墨烯导电面料，包括基材面料层、与基材面料复合的薄膜层、石墨烯涂覆层，所述的石墨烯涂覆层由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、粘合剂、增稠剂和水组成的涂层剂形成；
所述的防水剂，制备方法为：
1)乳化剂十二烷基硫酸钠、OS-15、TX-30以及去离子水于乳化釜中，搅拌、溶解，形成乳化剂溶液；另取BA、MMA、St及正十六烷搅拌混匀成混合单体；将混合单体加入乳化剂溶液中，搅拌乳化30min，超声处理15min，得乳化液；
2)在装有电动搅拌器、恒压滴液漏斗、回流冷凝管的反应器中加入十二烷基硫酸钠、乳化剂OS-15、去离子水，搅拌溶解，加入经表面改性的纳米SiO2，分散均匀，升温加热至78℃时，加入1/2体积乳化液及1/3体积引发剂水溶液，待反应温度稳定，乳液呈明显蓝光后，保温反应30min，然后升温至82℃，滴加剩余乳化液和1/3体积引发剂水溶液，2h内滴完；
3)滴加正十六烷和MMA、BA及如式1所示的有机硅单体混合液，滴加时间为1h左右，补加1/3体积引发剂水溶液，加料完毕后，升温到86℃，保温45min，停止加热，当反应体系温度降为40℃以下时出料，得防水剂乳液。
2.根据权利要求1所述的一种石墨烯导电面料，其特征在于：所述的基材面料为针织面料或梭织面料。
3.根据权利要求1所述的一种石墨烯导电面料，其特征在于：所述的薄膜为含石墨烯粉末的聚氨酯薄膜。
4.权利要求1所述一种石墨烯导电面料的制备方法，其特征在于：制备石墨烯导电面料时，先配置石墨烯涂层剂，在基材面料表面涂覆涂层剂，形成涂覆层，再于基材面料的另一侧，复合聚氨酯薄膜；所述的涂层剂由聚苯胺接枝石墨烯复合材料、分散剂、防水剂、增稠剂和粘合剂组成；
具体步骤如下：
1)、配置涂层剂；
2)、涂层：基材面料表面涂覆涂层剂、烘干、焙烘；
3)、复膜：先将基材面料、聚氨酯薄膜涂覆胶点，平整地叠加在一起，再移至压烫机中，然后设定热压时间和热压温度，待温度达到后，进行压烫，完成热压复膜。
5.根据权利要求4所述一种石墨烯导电面料的制备方法，其特征在于：所述的配置涂层剂步骤，具体为：在水中加入分散剂，搅拌均匀，缓慢加入聚苯胺接枝石墨烯复合材料，搅拌均匀后，超声分散30-60分钟，制备得到稳定的聚苯胺接枝石墨烯复合材料分散液，然后在搅拌下将防水剂、粘合剂乳液缓慢加入聚苯胺接枝石墨烯复合材料分散液中，搅拌均匀，最后以增稠剂调节粘度，即制得石墨烯涂层剂。
6.根据权利要求4所述一种石墨烯导电面料的制备方法，其特征在于：所述的防水剂，制备方法为：
1)乳化剂十二烷基硫酸钠、OS-15、TX-30以及去离子水于乳化釜中，搅拌、溶解，形成乳化剂溶液；另取BA、MMA、St及正十六烷搅拌混匀成混合单体；将混合单体加入乳化剂溶液中，搅拌乳化30min，超声处理15min，得乳化液；
2)在装有电动搅拌器、恒压滴液漏斗、回流冷凝管的反应器中加入十二烷基硫酸钠、乳化剂OS-15、去离子水，搅拌溶解，加入经表面改性的纳米SiO2，分散均匀，升温加热至78℃时，加入1/2体积乳化液及1/3体积引发剂水溶液，待反应温度稳定，乳液呈明显蓝光后，保温反应30min，然后升温至82℃，滴加剩余乳化液和1/3体积引发剂水溶液，2h内滴完；
3)滴加正十六烷和MMA、BA及如式1所示的有机硅单体混合液，滴加时间为1h左右，补加1/3体积引发剂水溶液，加料完毕后，升温到86℃，保温45min，停止加热，当反应体系温度降为40℃以下时出料，得防水剂乳液。
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