CN115262231B - Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof - Google Patents
Self-repairing self-cleaning electromagnetic shielding fabric coating and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 112
- 239000011248 coating agent Substances 0.000 title claims abstract description 107
- 239000004744 fabric Substances 0.000 title claims abstract description 41
- 238000004140 cleaning Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000004814 polyurethane Substances 0.000 claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 239000002077 nanosphere Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical compound OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 46
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 22
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 14
- 229940035024 thioglycerol Drugs 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 7
- 229960003638 dopamine Drugs 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001690 polydopamine Polymers 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 claims 1
- 230000006870 function Effects 0.000 abstract description 11
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002122 magnetic nanoparticle Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 239000000839 emulsion Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
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- 239000011664 nicotinic acid Substances 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920013657 polymer matrix composite Polymers 0.000 description 2
- 239000011160 polymer matrix composite Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 125000005581 pyrene group Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000219991 Lythraceae Species 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 230000001680 brushing effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- -1 tridecyl fluorooctyl Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- 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
- D06M11/80—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 boron or compounds thereof, e.g. borides
- D06M11/82—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 boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
Abstract
The invention discloses a self-repairing self-cleaning electromagnetic shielding fabric coating, a preparation method and application thereof, wherein the coating comprises the following raw materials in parts by weight: 40-80 parts of comb-shaped hydrophobic polyurethane, 2-20 parts of pomegranate-shaped magnetic silica nanospheres, 0.1-1 part of pyrene borate, 0.2-5 parts of graphene and 2-20 parts of mixed solution of ethanol and water. The invention provides a novel self-repairing self-cleaning electromagnetic shielding fabric coating, which is based on a pomegranate-shaped magnetic silicon dioxide nanosphere and self-repairing polyurethane, has an electromagnetic shielding function and a super-hydrophobic self-cleaning function, can self-repair damaged parts and recover functions, and solves the problems of poor electromagnetic shielding performance, no self-cleaning performance, durability and the like of an outdoor composite material. The method is simple, the preparation process is environment-friendly, and the method is easy to apply in large-area outdoor.
Description
Technical Field
The invention belongs to electromagnetic shielding coating materials, and particularly relates to a self-repairing self-cleaning electromagnetic shielding coating, and a preparation method and application thereof.
Background
With the explosive development of the fifth generation communication technology, human life and electronic communication devices have become inseparable. However, electromagnetic interference generated by these devices during operation not only affects the normal operation of nearby electronic devices, but also has side effects on human health. In order to protect precision equipment and human bodies from external radiation, it is very important to develop efficient self-repairing electromagnetic shielding materials. The polymer matrix composite material is widely applied to the field of electromagnetic shielding due to the advantages of low density, corrosion resistance, low cost, good processability and the like. At present, the electromagnetic property of the polymer matrix composite material can be effectively improved by adding conductive fillers such as carbon nano tubes, graphene, metal nano wires/particles, MXene and the likeShielding performance. Patent CN110698847A proposes a waterborne polyurethane-MXene electromagnetic shielding bionic nanocomposite film and a preparation method thereof, wherein the method utilizes a shell bionic strategy and uses Ti 3 C 2 T x /Ti 2 CT x MXene and water-based polyurethane with carbamate groups are used as raw materials, so that the high-efficiency electromagnetic shielding composite material film with good mechanical properties is constructed, and the film has excellent mechanical properties and good electromagnetic shielding properties. Patent CN111925642a proposes that firstly, a carbon nanotube aqueous dispersion is prepared, then a synthesized self-repairing cationic aqueous polyurethane emulsion is added into the carbon nanotube aqueous dispersion, and carbon nanotubes are coated on the surfaces of polyurethane emulsion particles by utilizing electrostatic adsorption interactions among ions with different charges, so that a self-repairing electromagnetic shielding composite material is finally obtained, and the material has electromagnetic shielding performance and mechanical performance, can realize certain self-repairing under the heating condition, and has higher repairing requirement and low repairing efficiency. Most polymer-based materials are inevitably susceptible to mechanical damage, thereby generating structural defects such as cracks, greatly reducing the physical properties and shortening the service life thereof.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a novel self-repairing self-cleaning electromagnetic shielding fabric coating, which not only has an electromagnetic shielding function, but also has a super-hydrophobic self-cleaning function based on the pomegranate-shaped magnetic silica nanospheres and the self-repairing polyurethane, and simultaneously, the coating can also self-repair damaged parts and recover the functions, thereby solving the problems of poor electromagnetic shielding performance, no self-cleaning performance, durability and the like of an outdoor composite material.
The invention also provides a preparation method and application of the self-repairing self-cleaning electromagnetic shielding fabric coating.
The technical scheme is as follows: in order to achieve the above purpose, the invention provides a self-repairing self-cleaning electromagnetic shielding fabric coating, which comprises the following raw materials in parts by weight: 40-80 parts of comb-shaped hydrophobic polyurethane, 2-20 parts of pomegranate-shaped magnetic silica nanospheres, 0.1-1 part of pyrene borate, 0.2-5 parts of graphene and 2-20 parts of mixed solution of ethanol and water; wherein the use of a garnet structure is more conducive to electromagnetic wave absorption.
The preparation method of the comb-shaped hydrophobic polyurethane comprises the following steps:
(1) Adding 10-60 parts of acetone and 0.05-1 part of dimethylphenylphosphine into 1-10 parts of thioglycerol and 1-20 parts of N- (1-pyrene) maleimide according to parts by weight, purifying after reaction, and drying to obtain a pyrene-containing dihydric alcohol monomer;
(2) Adding 20-80 parts of acetone and 0.05-2 parts of dimethylphenylphosphine into 1-15 parts of thioglycerol and 1-45 parts of tridecyl fluorooctyl methacrylate according to parts by weight, and purifying and drying after reacting to obtain a fluorine-containing dihydric alcohol monomer;
(3) Preheating 1-20 parts of isophorone diisocyanate, 2-60 parts of polycaprolactone and 20-80 parts of acetone in an oil bath, stirring to form a uniform solution, adding 0.05-2 parts of dibutyltin dilaurate, and reacting; then, 0.5 to 10 parts of fluorine-containing dihydric alcohol monomer and 0.5 to 15 parts of pyrene-containing dihydric alcohol monomer are respectively added, and the reaction is continuously kept; reducing the temperature of the oil bath, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuing to react to obtain the comb-shaped hydrophobic polyurethane (MPU).
Wherein, in the step (1), the reaction is carried out continuously for 1 to 8 hours at the temperature of 20 to 70 ℃, and the pyrene-containing dihydric alcohol monomer is obtained after purification and drying; continuously reacting for 1-8 hours at 20-80 ℃ in the step (2), purifying and drying to obtain a fluorine-containing dihydric alcohol monomer; preheating in an oil bath at 40-80 ℃ and keeping stirring to form a uniform solution, adding 0.05-2 parts of dibutyltin dilaurate, and keeping the reaction for 2-6 hours; then, 0.5 to 10 parts of fluorine-containing monomer and 0.5 to 15 parts of pyrene-containing monomer are respectively added, and the reaction is continued for 1 to 3 hours; and (3) regulating the temperature of the oil bath to 30-70 ℃, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting for 2-6 hours to obtain the comb-shaped hydrophobic polyurethane.
Preferably, the number average molecular weight of the polycaprolactone is 800-2000, and the number average molecular weight of the comb-shaped hydrophobic polyurethane is 10000-30000.
The preparation method of the pomegranate-shaped magnetic silica nanospheres comprises the following steps:
adding 0.1-2 parts of Fe into 0.5-2 parts of ammonia water and 10-60 parts of ethanol/deionized water mixture according to parts by weight 3 O 4 Dispersing the particles, dripping 0.3-3 parts of dopamine into the dispersion liquid under mechanical stirring, stirring and collecting Fe 3 O 4 Nano particles @ PDA, fe to be prepared 3 O 4 Dispersing the @ PDA nano particles in 20-150 parts of deionized water again, and adding 0.5-2 parts of ammonia water and 0.1-2 parts of surfactant; then, dropwise adding a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate into the dispersion liquid, magnetically absorbing and collecting a product after reaction, adding the product into 50-200 parts of ethanol, and carrying out reflux treatment to finally obtain the pomegranate-shaped magnetic silica nanospheres.
Wherein, the mixed solution of 10-50 parts of normal hexane and 5-40 parts of tetraethyl orthosilicate is dripped into the dispersion liquid, and the product is collected by a magnet, washed and dried after the reaction for 6-24 hours at the temperature of 25-65 ℃.
Preferably, wherein the Fe 3 O 4 The particle size of the particles is 20-500nm.
The preparation method of the self-repairing self-cleaning electromagnetic shielding fabric coating comprises the following steps:
adding 0.1-1 part of pyrene borate, 0.5-5 parts of garnet-shaped magnetic silica nanospheres and 0.2-2 parts of graphene (G) into a mixed solution containing ethanol and water according to parts by weight, washing and drying after reaction to obtain the garnet-shaped magnetic silica nanosphere modified graphene (mFe) 3 O 4 @SiO 2 -G)；
According to the weight portions, 100-200 portions of comb-shaped hydrophobic polyurethane and 5-50 portions of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene are uniformly mixed and dried to obtain the self-repairing self-cleaning electromagnetic shielding fabric coating.
Adding pyrene borate, the pomegranate-shaped magnetic silica nanospheres and graphene (G) into a mixed solution containing ethanol and water, reacting for 1-5h at 25-65 ℃, and washing and drying to obtain the pomegranate-shaped magnetic silica nanospheres modified graphene.
The self-repairing self-cleaning electromagnetic shielding fabric coating provided by the invention is widely applied to flexible sensors, intelligent wearable, self-healing materials and military stealth materials.
The self-repairing self-cleaning electromagnetic shielding fabric coating is formed by uniformly mixing comb-shaped hydrophobic polyurethane and pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, and then coating the mixture on the surface of the fabric and drying the mixture at a high temperature.
Preferably, the thickness of the coating is 1-20 mm, and the coating is performed on the surface of the fabric by at least one of brushing, roller coating, dip coating, spraying and curtain coating.
The self-repairing self-cleaning electromagnetic shielding coating provided by the invention not only solves the durability of the surface performance of the existing functional coating, but also solves the problems of low conductivity, general electromagnetic shielding performance, poor compatibility and the like of the existing polymer-based composite material. After the surface of the coating is subjected to physical abrasion or organic matter pollution, the dynamic disulfide bonds of the PMNs-FG/MPU fabric coating and pi-pi effect between graphene and PPU side chains can be stimulated by solar radiation or current due to excellent photo-thermal and electric heating characteristics, so that the fabric coating has excellent self-repairing performance, and the durability of the coating in outdoor use is ensured. Meanwhile, the fluoride modification of the graphene endows the film with excellent self-cleaning performance. The novel pomegranate-shaped magnetic microsphere PMNs wrapping a plurality of high-magnetic Fe3O4 nano particles show excellent electromagnetic shielding performance, and when the thickness of the coating is 1mm, the electromagnetic shielding energy efficiency (EMI SE) value of the coating is up to 50dB, and the requirements of commercial electromagnetic shielding materials are met. The method is simple, the preparation process is environment-friendly, and the method is easy to apply in large-area outdoor.
The self-repairing self-cleaning electromagnetic shielding coating provided by the invention is mainly combined with magnetic loss through dielectric loss of PMNs-FG, so that excellent electromagnetic shielding performance is obtained; on the basis of PMNs-FG, a micro-nano structure and modification of low-surface energy substances are formed on the surface of the coating, and the coating has excellent hydrophobicity to common liquid and can realize a self-cleaning function; inspired by gecko, the coating shows excellent self-repairing performance by utilizing a combination strategy of dynamic reversible disulfide bonds and pi-pi stacking interactions of polyurethane and PMNs-FG, and the action force of a conductive medium and resin is enhanced by forming pi-pi interactions between a special pyrene structure on a polyurethane branched chain and the surface of graphene. Therefore, the coating not only repairs the damaged surface structure, but also can realize higher repair efficiency, so that various properties of the repaired coating are more similar to those of the original coating.
In the preparation process, a fluorine-containing dihydric alcohol monomer, a pyrene-containing dihydric alcohol monomer and pyrene borate are used. Wherein the preparation of comb polyurethane: based on a typical prepolymer method, a diol monomer containing a special structure (fluorocarbon chain structure and pyrene ring structure) is obtained through a mercapto-alkene click reaction, and can react with isocyanate groups so as to successfully introduce the special structure into a polyurethane system in a branched form, and in addition, the self-repairing performance of the polyurethane is endowed through a chain extender containing disulfide bonds. Meanwhile, a novel self-repairing strategy is adopted: the self-healing properties of organic-inorganic composite coatings are often achieved by thermal migration of the resin, while the forces between the resin and the inorganic are small, so that the strategy is generally inefficient. According to the invention, the acting force between the resin and the conductive filler is improved in the modes of hydrogen bond, hydrophobic acting force, pi-pi effect and the like, so that the conductive filler is assisted to participate in the self-repairing process, the self-repairing efficiency of the material is improved, and the performance of the repaired material is more approximate to that of an initial state.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) Based on the special pomegranate-type structure of the magnetic microsphere, the coating can be endowed with excellent electromagnetic shielding property;
(2) The composite fabric coating shows excellent superhydrophobic self-cleaning property;
(3) The polyurethane-based comb structure can automatically repair damaged parts after the fabric coating is worn by external force or stretched and broken, and recover the mechanical, electromagnetic shielding and self-cleaning properties of the fabric coating;
(4) The preparation process of the composite fabric coating is environment-friendly and pollution-free;
(5) The coating can be coated on other base materials, and can be applied to the fields of intelligent wearable, flexible sensors, military stealth and the like.
Drawings
FIG. 1 is a FT-IR spectrum of a fluorine-containing diol monomer (M-PFM), a pyrene-containing diol monomer (M-NPM) and comb-like hydrophobic polyurethane (MPU) synthesized in example 4. The FT-IR spectrum can successfully prove that the fluorine-containing diol monomer and the pyrene-containing diol monomer are already connected into polyurethane and form comb-shaped and hydrophobic effects.
Fig. 2 is a TEM image of the garnet-shaped magnetic Particles (PMNs) in example 4. Several Fe's can be seen by TEM 3 O 4 The nano particles are coated by polydopamine PDA, and are hydrolyzed by tetraethyl orthosilicate TEOS to form SiO2 shells, and finally the magnetic nano particles with the garnet structures are formed.
Fig. 3 is an SEM image of the PMNs-supported graphene of example 4, from which it can be seen that the PMNs have been successfully supported on the graphene sheets.
Fig. 4 is a graph of the self-healing process (optical microscopy and water contact angle) of the composite fabric coating of example 4. The figure shows that the coating has cracks after damage and the superhydrophobic performance is lost, but the cracks of the coating disappear after repair, and the superhydrophobic performance of the damaged part is recovered.
FIG. 5 is a graph of the self-healing process of the hollow white coating of example 4, showing that the damaged coating cannot be healed.
FIG. 6 is a graph of the self-cleaning process of the composite fabric coating of example 4, showing that simulated stains on the surface of the coating can be removed by water droplets without residue, indicating that the coating surface has excellent self-cleaning properties.
Fig. 7 shows the electromagnetic shielding properties of the different fabric coatings in the X-band in example 4. Due to the high conductivity and good magnetic properties of PMNs-loaded graphene (PMNs-FG), the flexible PMNs-FG/MPU composite fabric coating exhibits excellent EMI shielding performance, which can reach about 50dB, compared to other coatings.
FIG. 8 is a graph showing the resistivity (a) of the PMNs-FG/PPU coating before and after self-repair, the stress-strain curve (b) of the PMNs-FG/PPU coating before and after self-repair, and the EMI SE value (c) of the PMNs-FG/PPU coating in the X-band before and after self-repair in example 4. After the PMNs-FG/PPU coating is repaired, the conductivity, mechanical property and electromagnetic shielding property of the PMNs-FG/PPU coating are recovered, which shows that the PMNs-FG/PPU coating has excellent self-repairing function.
Detailed Description
The invention is further illustrated by the following examples.
The raw materials used in the examples of the present invention are commercially available, or the same type of raw materials are commercially available.
The following examples were all calculated in parts by weight.
Example 1
(1) Adding 1 part of thioglycerol and 1 part of N- (1-pyrene) maleimide into a round-bottom flask, adding 10 parts of acetone as a solvent and 0.05 part of xylylphosphine as a catalyst, continuously reacting for 1h at 70 ℃, purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 1 part of thioglycerol and 1 part of tridecafluorooctyl methacrylate into a round-bottom flask, adding 20 parts of acetone as a solvent and 0.05 part of dimethylphenylphosphine as a catalyst, continuously reacting for 1h at 80 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
1 part of isophorone diisocyanate, 2 parts of polycaprolactone (molecular weight 2000) and 20 parts of acetone are added into a three-neck flask, and after being preheated in an oil bath at 80 ℃ and kept stirring to form a uniform solution, 0.05-2 parts of dibutyltin dilaurate is added and kept for reaction for 2 hours. Then, 0.5 part of fluorine-containing diol monomer and 0.5 part of pyrene-containing diol monomer are added respectively, and the reaction is continued for 1 hour. Finally, the temperature of the oil bath was adjusted to 70 ℃, 0.5 part of bis (2-hydroxyethyl) disulfide as a chain extender was added, and the reaction was continued for 2 hours to obtain comb-shaped hydrophobic polyurethane (MPU) (molecular weight: 30000 by GPC).
(2) 0.5 parts of ammonia water (concentration 25%), 10 parts of an ethanol/deionized water mixture (volume ratio of 1:2) were added to a three-necked flask, and then 0.1 parts of Fe was treated by ultrasonic waves 3 O 4 Particles (20 nm) are dispersed in the solution. Dropwise adding 0.3 Part of Dopamine (PDA) into the dispersion liquid under mechanical stirring, continuously stirring for 2h, and collecting Fe 3 O 4 PDA nanoparticles were washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 20 parts deionized waterTo the mixture, 0.5 parts of aqueous ammonia (concentration: 25%) and 0.1 parts of cetyltrimethylammonium chloride were added. Subsequently, a mixed solution of 10 parts of n-hexane and 5 parts of tetraethyl orthosilicate was added dropwise to the above dispersion, reacted at 65 ℃ for 6 hours, and the product was collected by a magnet, washed and dried. Adding the product into 50 parts of ethanol, and refluxing at 65 ℃ for 2 hours to remove the template to finally obtain the pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.1 part of 1-pyrene borate and 0.5 part of mFe 3 O 4 @SiO 2 And 0.2 part of graphene (G) was added to 2 parts of a mixed solution containing ethanol and water (volume ratio=1:1). After reacting for 1h at 65 ℃, washing and drying to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
100 parts of comb-shaped hydrophobic polyurethane and 5 parts of pomegranate-shaped magnetic silica nanosphere modified graphene are uniformly mixed, coated on the surface of a fabric and dried at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 20mm.
Example 2
(1) Adding 10 parts of thioglycerol and 20 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 60 parts of acetone as a solvent and 1 part of xylylphosphine as a catalyst, continuously reacting for 8 hours at 20 ℃, purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
15 parts of thioglycerol and 45 parts of tridecafluorooctyl methacrylate are added into a round-bottom flask, 80 parts of acetone is added as a solvent, 2 parts of dimethylphenylphosphine is used as a catalyst, the reaction is continued for 8 hours at 20 ℃, and the fluorine-containing dihydric alcohol monomer is obtained after purification and drying.
20 parts of isophorone diisocyanate, 60 parts of polycaprolactone (molecular weight 1000) and 80 parts of acetone are added into a three-necked flask, and after being preheated in an oil bath at 40 ℃ and kept stirring to form a uniform solution, 2 parts of dibutyltin dilaurate are added and kept reacting for 6 hours. Then, 10 parts of fluorine-containing diol monomer and 15 parts of pyrene-containing diol monomer are added respectively, and the reaction is continued for 3 hours. Finally, the temperature of the oil bath is adjusted to 30 ℃, 5 parts of chain extender bis (2-hydroxyethyl) disulfide is added, and the reaction is continued for 6 hours, so that comb-shaped hydrophobic polyurethane (MPU) is obtained (the molecular weight of the comb-shaped hydrophobic polyurethane is 15000 through GPC test).
(2) 2 parts of ammonia water (concentration 25%), 60 parts of an ethanol/deionized water mixture (volume ratio of 1:2) were added to a three-necked flask, and 2 parts of Fe were then added by ultrasonic treatment 3 O 4 Particles (500 nm) are dispersed in the solution. Dropwise adding 3 Parts of Dopamine (PDA) into the dispersion liquid under mechanical stirring, continuously stirring for 10 hours, and collecting Fe 3 O 4 PDA nanoparticles were washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 150 parts deionized water and added with a solution containing 2 parts ammonia (25% strength) and 2 parts cetyl trimethylammonium bromide. Subsequently, a mixed solution of 50 parts of n-hexane and 40 parts of tetraethyl orthosilicate was added dropwise to the above dispersion, reacted at a temperature of 25 ℃ for 24 hours, and the product was collected by a magnet, washed and dried. Adding the product into 200 parts of ethanol, and refluxing at 65 ℃ for 8 hours to remove the template to finally obtain the pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 1 part of 1-pyrene borate, 5 parts of mFe 3 O 4 @SiO 2 And 2 parts of graphene (G) were added to 20 parts of a mixed solution containing ethanol and water (volume ratio=1:1). After reacting for 5 hours at 25 ℃, washing and drying to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
After 200 parts of comb-shaped hydrophobic polyurethane and 50 parts of pomegranate-shaped magnetic silica nanosphere modified graphene are uniformly mixed, the mixture is coated on the surface of a fabric and dried for 8 hours at 80 ℃ to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 8mm.
Example 3
(1) 3 parts of thioglycerol and 7 parts of N- (1-pyrene) maleimide are added into a round-bottom flask, 20 parts of acetone is added as a solvent, 0.1 part of xylylphosphine is used as a catalyst, the reaction is continued for 5 hours at 40 ℃, and the pyrene-containing dihydric alcohol monomer is obtained after purification and drying.
Adding 4 parts of thioglycerol and 10 parts of tridecafluorooctyl methacrylate into a round-bottom flask, adding 30 parts of acetone as a solvent and 0.15 part of dimethylphenylphosphine as a catalyst, continuously reacting for 5 hours at 40 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
8 parts of isophorone diisocyanate, 20 parts of polycaprolactone (molecular weight 1500) and 40 parts of acetone are added into a three-necked flask, and after being preheated in an oil bath at 50 ℃ and kept stirring to form a uniform solution, 0.5 part of dibutyltin dilaurate is added and kept for reaction for 3 hours. Then, 2 parts of fluorine-containing diol monomer and 5 parts of pyrene-containing diol monomer are added respectively, and the reaction is continued for 2 hours. Finally, the temperature of the oil bath is adjusted to 40 ℃,2 parts of chain extender bis (2-hydroxyethyl) disulfide is added, and the reaction is continued for 3 hours, thus obtaining comb-shaped hydrophobic polyurethane (MPU) (the molecular weight of the comb-shaped hydrophobic polyurethane is 25000 by GPC).
(2) 0.8 parts of ammonia water (concentration 25%), 30 parts of an ethanol/deionized water mixture (volume ratio of 1:2) were added to a three-necked flask, and then 0.8 parts of Fe was treated by ultrasonic waves 3 O 4 Particles (100 nm) are dispersed in the solution. Dropwise adding 1.2 Parts of Dopamine (PDA) into the dispersion liquid under mechanical stirring, continuously stirring for 5h, and collecting Fe 3 O 4 PDA nanoparticles were washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 60 parts deionized water and added with an aqueous ammonia solution (25% strength) containing 0.8 parts, 0.8 parts octadecyl trimethyl ammonium chloride. Subsequently, a mixed solution of 20 parts of n-hexane and 15 parts of tetraethyl orthosilicate was added dropwise to the above dispersion, reacted at a temperature of 30 ℃ for 10 hours, and the product was collected by a magnet, washed and dried. Adding the product into 90 parts of ethanol, and refluxing at 65 ℃ for 4 hours to remove the template to finally obtain the pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.5 part of 1-pyrene borate, 2 parts of mFe 3 O 4 @SiO 2 And 0.8 part of graphene (G) was added to 8 parts of a mixed solution containing ethanol and water (volume ratio=1:1). After reacting for 4 hours at 35 ℃, washing and drying to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene (PMNs)-FG)(mFe 3 O 4 @SiO 2 -G)。
After 120 parts of comb-shaped hydrophobic polyurethane and 20 parts of pomegranate-shaped magnetic silica nanosphere modified graphene are uniformly mixed, the mixture is coated on the surface of a fabric and dried for 8 hours at 80 ℃ to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 14mm.
Example 4
(1) Adding 5 parts of thioglycerol and 11 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 30 parts of acetone as a solvent and 0.4 part of dimethylphenylphosphine as a catalyst, continuously reacting for 3 hours at 50 ℃, purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 8 parts of thioglycerol and 22 parts of tridecafluorooctyl methacrylate into a round-bottom flask, adding 50 parts of acetone as a solvent and 1 part of xylylphosphine as a catalyst, continuously reacting for 3 hours at 50 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
11 parts of isophorone diisocyanate, 32 parts of polycaprolactone (molecular weight: 1200) and 50 parts of acetone are added to a three-necked flask, and after being preheated in an oil bath at 60℃and kept stirring to form a homogeneous solution, 1.2 parts of dibutyltin dilaurate are added and kept for 4 hours. Then, 5 parts of fluorine-containing diol monomer and 8 parts of pyrene-containing diol monomer are added respectively, and the reaction is continued for 3 hours. Finally, the temperature of the oil bath is adjusted to 50 ℃, 3 parts of chain extender bis (2-hydroxyethyl) disulfide is added, and the reaction is continued for 4 hours, thus obtaining comb-shaped hydrophobic polyurethane (MPU) (the molecular weight of the MPU is 20000 according to GPC test).
(2) 1.2 parts of ammonia water (concentration 25%), 40 parts of an ethanol/deionized water mixture (volume ratio of 1:2) were added to a three-necked flask, and then 1.2 parts of Fe was treated by ultrasonic waves 3 O 4 Particles (250 nm) are dispersed in the solution. 1.6 Parts of Dopamine (PDA) is added dropwise to the dispersion liquid under mechanical stirring, and after continuous stirring for 6 hours, fe is collected 3 O 4 PDA nanoparticles were washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 80 parts deionized water and added with a solution containing 1.2 parts ammonia (25% strength), 1.2 parts docosyltrimethyl chlorideAnd (5) ammonium. Subsequently, a mixed solution of 30 parts of n-hexane and 22 parts of tetraethyl orthosilicate was added dropwise to the above dispersion, reacted at a temperature of 35 ℃ for 14 hours, and the product was collected by a magnet, washed and dried. Adding the product into 110 parts of ethanol, and refluxing at 65 ℃ for 5 hours to remove the template to finally obtain the pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.6 part of 1-pyrene borate, 2.5 parts of mFe 3 O 4 @SiO 2 And 1 part of graphene (G) was added to 10 parts of a mixed solution containing ethanol and water (volume ratio=1:1). After reacting for 4 hours at 40 ℃, washing and drying to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
(4) After 150 parts of comb-shaped hydrophobic polyurethane and 26 parts of pomegranate-shaped magnetic silica nanosphere modified graphene are uniformly mixed, the mixture is coated on the surface of a fabric and dried for 8 hours at 80 ℃ to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 1mm.
Example 5
(1) Adding 8 parts of thioglycerol and 15 parts of N- (1-pyrene) maleimide into a round-bottom flask, adding 50 parts of acetone as a solvent and 0.8 part of xylylphosphine as a catalyst, continuously reacting for 2 hours at 60 ℃, purifying and drying to obtain the pyrene-containing dihydric alcohol monomer.
Adding 12 parts of thioglycerol and 40 parts of tridecafluorooctyl methacrylate into a round-bottom flask, adding 70 parts of acetone as a solvent and 1.5 parts of xylylphosphine as a catalyst, continuously reacting for 2 hours at 60 ℃, purifying and drying to obtain the fluorine-containing dihydric alcohol monomer.
14 parts of isophorone diisocyanate, 50 parts of polycaprolactone (molecular weight 800) and 70 parts of acetone are added to a three-necked flask, and after being preheated in an oil bath at 70 ℃ and kept stirring to form a uniform solution, 1.6 parts of dibutyltin dilaurate is added and kept for reaction for 3 hours. Then, 8 parts of fluorine-containing diol monomer and 12 parts of pyrene-containing diol monomer are added respectively, and the reaction is continued for 2 hours. Finally, the temperature of the oil bath is adjusted to 50 ℃, 4 parts of chain extender bis (2-hydroxyethyl) disulfide is added, and the reaction is continued for 5 hours, thus obtaining comb-shaped hydrophobic polyurethane (MPU) (the molecular weight of the MPU is 10000 through GPC test).
(2) 1.5 parts of ammonia water (concentration 25%), 50 parts of an ethanol/deionized water mixture (volume ratio of 1:2) were added to a three-necked flask, and then 1.5 parts of Fe was treated by ultrasonic waves 3 O 4 Particles (400 nm) are dispersed in the solution. Dropwise adding 2 Parts of Dopamine (PDA) into the dispersion liquid under mechanical stirring, continuously stirring for 8 hours, and collecting Fe 3 O 4 PDA nanoparticles were washed with deionized water and dried. Fe to be prepared 3 O 4 The @ PDA nanoparticles were redispersed in 120 parts deionized water and added with a solution containing 1.5 parts ammonia (25% strength) and 1.5 parts cetyl trimethylammonium bromide. Subsequently, a mixed solution of 40 parts of n-hexane and 30 parts of tetraethyl orthosilicate was added dropwise to the above dispersion, reacted at 45 ℃ for 16 hours, and the product was collected by a magnet, washed and dried. Adding the product into 150 parts of ethanol, and refluxing at 65 ℃ for 6 hours to remove the template to finally obtain the pomegranate-shaped magnetic silica nanospheres (PMNs) (mFe) 3 O 4 @SiO 2 )。
(3) 0.8 part of 1-pyrene borate, 4 parts of mFe 3 O 4 @SiO 2 And 1.5 parts of graphene (G) were added to 15 parts of a mixed solution containing ethanol and water (volume ratio=1:1). After reacting for 2 hours at 45 ℃, washing and drying to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene (PMNs-FG) (mFe) 3 O 4 @SiO 2 -G)。
180 parts of comb-shaped hydrophobic polyurethane and 45 parts of pomegranate-shaped magnetic silica nanosphere modified graphene are uniformly mixed, coated on the surface of a fabric, and dried at 80 ℃ for 8 hours to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating (PMNs-FG/MPU), wherein the thickness of the coating is 5mm.
Test example 1
The testing method comprises the following steps:
(1) Fourier infrared spectroscopy test (FT-IR)
The chemical structures of the monomer and MPU in example 4 were tested by Fourier infrared spectroscopy, and the ATR total reflection test was performed at room temperature in the wavelength range of 500-4000cm -1 。
The FT-IR spectrum of FIG. 1 successfully demonstrates that the fluorine-containing diol monomer and the pyrene-containing diol monomer have been incorporated into the polyurethane and formed a comb-like and hydrophobic effect.
(2) Transmission electron microscope Test (TEM)
The core-shell structure of the PMNs of example 4 was observed with a transmission electron microscope and the test voltage was 200kV.
Several Fe's can be seen by TEM of FIG. 2 3 O 4 The nano particles are coated by polydopamine PDA and are hydrolyzed by tetraethyl orthosilicate TEOS to form SiO 2 And a shell, and finally, the magnetic nano particles with the pomegranate-shaped structures are formed, wherein a plurality of nano ferroferric oxide particles similar to pomegranate seeds are arranged in the balls.
(3) Scanning Electron Microscope (SEM)
The microscopic morphology of the PMNs-FG of example 4 was tested using a scanning electron microscope at a test voltage of 5kV.
It can be seen from the SEM of fig. 3 that a plurality of magnetic nanoparticles of garnet structure have been successfully loaded onto the graphene sheets.
(4) Self-healing performance test
Blank PU coating: the preparation method is the same as in example 4, except that: no chain extender hydroxyethyl disulfide was added.
A blade is used for scribing a notch with the length of 2cm and the depth of 0.5cm on the surfaces of the blank PU coating and the PMNs-FG/MPU composite coating respectively, then the notch is placed in a 50 ℃ oven, and the appearance change of scratches in the self-repairing process of the blank PU coating and the PMNs-FG/MPU composite coating in the example 4 is recorded by adopting an optical microscope, wherein the multiples of an objective lens and an eyepiece are respectively multiplied by 50 and multiplied by 10.
The self-healing process diagram (optical microscopy and water contact angle) of the composite fabric coating is shown in fig. 4. Figure 4 shows that the coating has cracks after damage and the superhydrophobic performance is lost, but the cracks of the coating disappear after repair, and the superhydrophobic performance of the damaged part is recovered.
FIG. 5 shows that the blank PU coating is not repaired at 50 ℃ for 15 minutes, which indicates that the PU coating has no self-repairing function, and the hydroxyethyl disulfide plays a main role in the self-repairing function of the coating.
(5) Super-hydrophobic and self-cleaning properties
The hydrophobicity of the coating prepared in example 4 was evaluated using a contact angle meter DSA 100. Firstly, placing the coated fabric on a horizontal table top, dripping liquid drops, observing and recording the shapes of the liquid drops, and obtaining the contact angle through software simulation calculation. When the rolling angle is tested, the horizontal table top is replaced by an inclined plane with an adjustable angle, the inclined plane is set to a proper angle, and whether the water drops can freely slide down from the coating is observed.
Fig. 4 shows that the scratch coating loses the superhydrophobic performance in the damaged area, the contact angle is reduced to 115.06 degrees, and the contact angle of the damaged area is restored to 153.6 degrees after self-repairing, so that the superhydrophobic performance of the coating is restored, and the coating has self-repairing superhydrophobic performance.
Fig. 6 shows that the simulated stain on the surface of the coating can be removed by water droplets without residue, indicating that the surface of the coating has excellent self-cleaning properties.
(6) Electromagnetic shielding performance test
The S-parameters of the sample of example 4 were measured by the waveguide method using a vector network analyzer in the X-band frequency range according to ASTM D5568-08. The S parameter corresponds to transmission (S12 and S21) and reflection (S11 and S22) of transverse electromagnetic waves. The self-healing composite film was cut into 22.86mm by 10.16mm samples for testing. R, A and T values are calculated from the S parameters. R and T may be represented as r= |s11| 2 ＝|S22| 2 And t= |s12| 2 ＝|S21| 2 . Using the formula a+r+t=1, a can be calculated from the results of R and T. Thus, the reflectance and the effective absorbance can be easily defined as SE R = -10log (1-R) and SE A ＝-10log[T/(1-R)]. For SE>15dB, multiple reflection (SE M ) Negligible.
Due to the high conductivity and good magnetic properties of PMNs-loaded graphene (PMNs-FG), compared to other coatings as shown in fig. 7 (magnetic nanoparticle PMNs of garnet structure, graphene and comb polyurethane blend coating Fe 3 O 4 NPs/FG/MPU, graphene and comb polyurethane blend coating FG/MPU, magnetic nanoparticle with pomegranate-shaped structure and comb polyurethane blendCoating PMNs/MPU, pure comb polyurethane coating MPU), the flexible PMNs-FG/MPU composite fabric coating exhibits excellent EMI shielding performance, which can reach about 50dB of EMI effectiveness.
Wherein, the magnetic nanoparticle PMNs with the pomegranate-shaped structure is the product of the step (2) in the embodiment 4;
the nanoparticle PMNs-modified graphene and comb-shaped polyurethane blending coating PMNs-FG/MPU is the coating prepared in the embodiment 4 of the invention;
PMNs (permanent magnet synchronous motor), graphene and comb-shaped polyurethane direct blending coating Fe of magnetic nanoparticle with pomegranate-shaped structure 3 O 4 NPs/FG/MPU is the method of example 4 according to the present invention, without using the coating prepared in step (3);
the graphene and comb polyurethane blend coating FG/MPU is a coating prepared by the method of the step (4) directly with graphene after preparing comb hydrophobic polyurethane (MPU) by the method of the embodiment 4 of the invention;
the PMNs/MPU of the magnetic nanoparticle and comb polyurethane blend coating with the pomegranate-shaped structure is the coating prepared by the method of the step (4) directly from the comb hydrophobic polyurethane (MPU) and the magnetic silica nanospheres (PMNs) without using the step (3);
the pure comb polyurethane coating MPU is a coating prepared by the product of step (1) of example 4 of the present invention.
(7) The resistivity of the PMNs-FG/MPU coating prepared in example 4 before and after multiple self-repairs was tested using a four-probe resistance tester; testing stress strain curves before and after self-repairing of the PMNs-FG/MPU composite coating by using a universal stretcher, wherein the stretching speed is 0.5cm/s; the S parameters before and after self-healing of pmns-FG/PPU coatings were measured by the waveguide method using a vector network analyzer in the X-band frequency range according to ASTM D5568-08. FIG. 8 is a graph showing the resistivity of the PMNs-FG/PPU coating before and after self-repair, the stress-strain curves of the PMNs-FG/PPU coating before and after self-repair, and the EMI SE values in the X band of the PMNs-FG/PPU coating before and after self-repair in example 4. After the PMNs-FG/PPU coating is repaired, the conductivity, mechanical property and electromagnetic shielding property of the PMNs-FG/PPU coating are recovered, which shows that the PMNs-FG/PPU coating has excellent self-repairing function.
Claims (7)
1. The preparation method of the self-repairing self-cleaning electromagnetic shielding fabric coating is characterized by comprising the following steps of:
adding 0.1-1 part of pyrene borate, 0.5-5 parts of pomegranate-shaped magnetic silica nanospheres and 0.2-2 parts of graphene into a mixed solution containing ethanol and water according to parts by weight, and washing and drying after reaction to obtain the pomegranate-shaped magnetic silica nanosphere modified graphene;
according to parts by weight, uniformly mixing 100-200 parts of comb-shaped hydrophobic polyurethane and 5-50 parts of pomegranate-shaped magnetic silicon dioxide nanosphere modified graphene, and drying to obtain a self-repairing self-cleaning electromagnetic shielding fabric coating;
the preparation of the comb-shaped hydrophobic polyurethane comprises the following steps:
(1) Adding 10-60 parts of acetone and 0.05-1 part of dimethylphenylphosphine into 1-10 parts of thioglycerol and 1-20 parts of N- (1-pyrene) maleimide according to parts by weight, purifying after reaction, and drying to obtain a pyrene-containing dihydric alcohol monomer;
(2) Adding 20-80 parts of acetone and 0.05-2 parts of dimethylphenylphosphine into 1-15 parts of thioglycerol and 1-45 parts of tridecyl methacrylate and performing reaction, purifying and drying to obtain a fluorine-containing dihydric alcohol monomer;
(3) Preheating 1-20 parts of isophorone diisocyanate, 2-60 parts of polycaprolactone and 20-80 parts of acetone in an oil bath, stirring to form a uniform solution, adding 0.05-2 parts of dibutyltin dilaurate, and reacting; then, 0.5 to 10 parts of fluorine-containing dihydric alcohol monomer and 0.5 to 15 parts of pyrene-containing dihydric alcohol monomer are respectively added, and the reaction is continuously kept; reducing the temperature of an oil bath, adding 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide, and continuously reacting to obtain comb-shaped hydrophobic polyurethane;
the preparation method of the pomegranate-shaped magnetic silica nanospheres comprises the following steps:
adding 0.1-2 parts of Fe into 0.5-2 parts of ammonia water and 10-60 parts of ethanol/deionized water mixture according to parts by weight 3 O 4 Dispersing the particles to obtain a dispersion liquid I, dropwise adding 0.3-3 parts of dopamine into the dispersion liquid I under mechanical stirring, and collecting tetraoxideComposite nano particle Fe of tri-iron/poly-dopamine 3 O 4 @PDA, composite nanoparticle Fe to be prepared 3 O 4 Dispersing the @ PDA again in 20-150 parts of deionized water, and adding 0.5-2 parts of ammonia water and 0.1-2 parts of surfactant to obtain a second dispersion; then, dropwise adding 10-50 parts of mixed solution of n-hexane and 5-40 parts of tetraethyl orthosilicate into the dispersion liquid II, magnetically absorbing and collecting products after reaction, adding the products into 50-200 parts of ethanol, and carrying out reflux treatment to finally obtain the pomegranate-shaped magnetic silica nanospheres.
2. The preparation method according to claim 1, wherein in the step (1), the pyrene-containing diol monomer is obtained by continuous reaction at 20-70 ℃ for 1-8h, purification and drying; continuously reacting at 20-80 ℃ in the step (2) for 1-8h, purifying and drying to obtain a fluorine-containing dihydric alcohol monomer; preheating in an oil bath at 40-80 ℃ and keeping stirring to form a uniform solution, adding 0.05-2 parts of dibutyltin dilaurate, and keeping the reaction of 2-6h; then, 0.5 to 10 parts of fluorine-containing monomer and 0.5 to 15 parts of pyrene-containing monomer are respectively added, and the reaction is continued for 1 to 3 hours; the temperature of the oil bath is adjusted to 30-70 ℃, 0.5-5 parts of chain extender bis (2-hydroxyethyl) disulfide is added, and the comb-shaped hydrophobic polyurethane is obtained after continuous reaction of 2-6 h.
3. The method of claim 1, wherein the comb hydrophobic polyurethane has a number average molecular weight of 10000-30000.
4. The preparation method according to claim 1, wherein a mixed solution of 10-50 parts of n-hexane and 5-40 parts of tetraethyl orthosilicate is added dropwise to the dispersion liquid II, and after reacting at a temperature of 25-65 ℃ for 6-24h, the product is collected by a magnet, washed and dried.
5. The preparation method of claim 1, wherein pyrene borate, the garnet-shaped magnetic silica nanospheres and graphene are added into a mixed solution containing ethanol and water, and after the mixed solution reacts for 1-5 hours at 25-65 ℃, the garnet-shaped magnetic silica nanospheres modified graphene is obtained after washing and drying.
6. An application of the self-repairing self-cleaning electromagnetic shielding fabric coating prepared by the preparation method of claim 1 in flexible sensors, intelligent wearable self-healing materials and military stealth materials.
7. The application of claim 6, wherein the self-repairing self-cleaning electromagnetic shielding fabric coating is prepared by uniformly mixing comb-shaped hydrophobic polyurethane and pomegranate-shaped magnetic silica nanosphere modified graphene, coating the mixture on the surface of the fabric, and drying at a high temperature.
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