CN101165127A - Water polyurethane electric conduction paint containing carbon nano-tube and preparation method thereof - Google Patents
Water polyurethane electric conduction paint containing carbon nano-tube and preparation method thereof Download PDFInfo
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- CN101165127A CN101165127A CNA2007100469048A CN200710046904A CN101165127A CN 101165127 A CN101165127 A CN 101165127A CN A2007100469048 A CNA2007100469048 A CN A2007100469048A CN 200710046904 A CN200710046904 A CN 200710046904A CN 101165127 A CN101165127 A CN 101165127A
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- carbon nanotube
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- electric conduction
- containing carbon
- carbon nano
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 61
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003973 paint Substances 0.000 title claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 25
- 239000004814 polyurethane Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 8
- -1 solubility promoter Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 235000017858 Laurus nobilis Nutrition 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 235000005212 Terminalia tomentosa Nutrition 0.000 claims description 2
- 244000125380 Terminalia tomentosa Species 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920013701 VORANOL™ Polymers 0.000 claims description 2
- PTABKUAUBJZSEC-UHFFFAOYSA-N acetylene ethane-1,2-diol Chemical compound C#C.OCCO PTABKUAUBJZSEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003054 adipate polyester Polymers 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 239000011231 conductive filler Substances 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229960000878 docusate sodium Drugs 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XOMPUFACNHSNPC-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1C XOMPUFACNHSNPC-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Images
Abstract
The present invention belongs to the field of chemical technology, and is especially one kind of conducting water soluble polyurethane paint containing carbon nanotube and its preparation process. The conducting paint is prepared through the first modifying carbon nanotube chemically for the surface to carry hydroxyl group, carboxyl group or amino group; the subsequent introducing to polyester polyol or isocyanate terminated polyurethane pre-polymer through chemical bonding and self-emulsifying to prepare water soluble polyurethane dispersoid containing carbon nanotube; and final adding deionized water and assistants through high speed stirring to obtain the conducting paint. The conducting paint can form coating with volume resistivity of 1x10<-5>-4x10<-4. ohm.cm, surface resistivity of 1x10<-1>-2x10<2> ohm, adhesion of 0 grade, shielding effectiveness of 70-85 dB, and long term stability, and has wide application.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of water polyurethane electric conduction paint containing carbon nano-tube and preparation method thereof.
Background technology
In recent years, along with electronization, informationalized high speed development, greatly popularizing of the e-machine of built-in information micro treatmenting device, and the arithmetic speed of CPU high speed more and more, consequent electromagnetic compatibility, information security and noise pollution problem are also more and more serious.From domestic external, one of main method of solution is exactly to adopt the electromagnetic radiation protection material that radiation is protected at present.In various electromagnetic radiation protection materials, coating with its convenience, light weight, do not take up space and with numerous advantages become wherein outstanding person such as matrix is integrated, be widely used in the electromagnetic radiation protection of each electronic product, device, system.
Existing electrically conducting coating, the overwhelming majority is a solvent based coating, it mainly is made up of conductive filler material, resin, thinner and additive etc.Conductive filler material generally is non-metal powders such as metal-powders such as silver, copper, nickel, conductive carbon black, graphite and oxide compound.Resin commonly used has Resins, epoxy, urethane, resol, acrylic resin etc.Generally speaking, mainly there are two deficiencies in traditional electrically conducting coating technology of preparing, and first conductive filler material is not ideal enough, and this shows that mainly conductive effect is bad or conductivity is unstable or costs an arm and a leg; It two is that existing electrically conducting coating is a solvent with the organic solvent all almost, and environmental pollution is serious.Along with information industry with the arithmetic speed of mobile phone, computer high speed more and more, require shielded radio frequency and electromagnetic interference, environment protection requirement is also more and more higher simultaneously, therefore, the exploitation of the waterborne conductive coating of environment-friendly high-efficiency is just very urgent.
Prior art CN1760294A (2006.4.19) and CN1730571A (2006.2.8) are to be that conductive agent joins mixed waterborne conductive coating in emulsion, water, solubility promoter and the additive with silver powder or mixed valence metal oxide, although these coating all have good electrical conductivity, shielding properties and sticking power, this coating remains further to be developed in room temperature storage stability and the aspects such as dispersing uniformity of conductive particle in resin.We can say, the package stability of waterborne conductive coating and the conductive particle dispersing uniformity in resin etc. rise to an insoluble always difficult problem in the prior art.
Prior art CN1775881A (2006.5.24) makes a kind of nano-sized carbon electrically conducting coating with high stability with nano-sized carbon, silicone resin and organic solvent, but compare with CN1730571A (2006.2.8) etc. with CN1760294A (2006.4.19), its conductive coating performance will reduce by 2 and 3 above orders of magnitude respectively, it is not very good aspect shielding properties, but also has used the dimethylbenzene of 10-50%.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, all good waterborne conductive coating such as a kind of electroconductibility, shielding, package stability and the conductive particle dispersing uniformity in resin and preparation method thereof is provided.
Waterborne conductive coating provided by the invention is a kind of water polyurethane electric conduction paint containing carbon nano-tube.This electrically conducting coating is prepared by following method: at first carbon nanotube is carried out chemically modified, make its surface be with a certain amount of hydroxyl, carboxyl or amido, method by chemical bonding is incorporated into this carbon nanotube in polyester polyol or the isocyanate-terminated base polyurethane prepolymer for use as then, prepares the water polyurethane electric conduction paint dispersion of described carbon nanotubes again by self-emulsification.
The preparation method of the water polyurethane electric conduction paint containing carbon nano-tube that the present invention proposes is as follows:
(1) be 3 by volume with 100～1000mg multi-walled carbon nano-tubes adding 150ml vitriol oil and concentrated nitric acid: 0.8-3: in the 1.2 mixed strong acids solution of forming, sonic oscillation was handled 3～12 hours, pour in the deionized water, and leave standstill (as 12-18 hour) more than 12 hours, filter and be washed to neutrality, oven dry obtains the carbon nanotube with carboxyl again;
(2) under nitrogen protection, the carbon nanotube of the above-mentioned band carboxyl of 80～800mg is placed the excessive thionyl chloride 12～72h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 50～500mg is dispersed in the anhydrous propanone, drip several (dripping) fresh pyridines or triethylamine as 3-10, under 55-65 ℃ of condition, dropwise Dropwise 5～20ml concentration is the diamine of 0.005～0.025g/ml or the acetone soln of dibasic alcohol, the dropping time is not less than 60 minutes (for example 60-80 minute), dropwised successive reaction 4～72 hours, excessive diamine or dibasic alcohol are removed with a large amount of acetone thorough washing, centrifuging, vacuum-drying obtains containing the carbon nanotube of amino or hydroxyl isoreactivity group;
(4) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent are with 100: 300～400: 20-60: 0.05～5: the mixed of 300～500 (weight) is even, be warming up to 55-65 ℃, reacted 6-12 hour, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer;
(5) with above-mentioned isocyanate-terminated polyurethane prepolymer, contain carbon nanotube, catalyzer and the organic solvent of amino or hydroxyl isoreactivity group, ratio with 100: 1～50: 0.5～2: 50～200 (weight) mixes, temperature is controlled at 55-65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes.Measure 200～500ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 30～60 minutes, and temperature is 45～50 ℃.After dropwising, temperature is 33-36 ℃, continues reaction 25-35 minute again, after vacuum filtration is removed acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes.
(6) with above-mentioned carbon nanotubes aqueous polyurethane dispersion and deionized water and auxiliary agent (as solubility promoter, wetting agent, membrane-forming agent etc.) mixing, at ambient temperature, stirred 30～60 minutes, add thickening material then, continue to stir 15～60 minutes, make water polyurethane electric conduction paint containing carbon nano-tube.
Among the present invention, described diamine can be quadrol, propylene diamine, 1,4-butanediamine or hexanediamine etc.; Described dibasic alcohol can be ethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,2-pentanediol, 1,5 pentanediol, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol, 3-chloro-1,2-propylene glycol or decanediol etc.; Said vulcabond can be that aromatic diisocyanate is (as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate), or aliphatic diisocyanate (as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond etc.).Said polyester polyol can be adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, high-molecular-weight poly ester polyol, the extraordinary polyester polyol of being with side group or PCDL etc.; Said catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Said organic solvent can be acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide etc.
Among the present invention, described solubility promoter can be N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide etc.
Among the present invention, described thickening material can be Polyacrylic Acid Thickener, cellulose thickener or polyurethane associative thickener etc.;
Among the present invention, described wetting agent can be dialkyl group (octyl group, hexyl, butyl) sulfosuccinate, alkyl how sodium sulfonate, Viscotrol C hydrosulfate, sodium laurylsulfonate, sulfuric acid laurel tallow, oleic acid butyl ester hydrosulfate, alkylphenol polyvinyl ether, Voranol EP 2001, polyoxyethylene glycol alkyl ester, polyoxyethylene glycol alkyl aryl ether, acetylene ethylene glycol etc. or polyether modified siloxane etc.
Among the present invention, described membrane-forming agent can be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether etc.;
The water polyurethane electric conduction paint containing carbon nano-tube of the present invention's preparation, its volume specific resistance magnitude range of filming is 1 * 10
-5～4 * 10
-4Ω cm, the surface resistivity magnitude range is 1 * 10
-1～2 * 10
2Ω, 0 grade of sticking power, effectiveness of shielding are 70～85dB.The result places back (for example 3 months) for a long time, and this water-borne coatings still keeps stable and do not have generation such as sedimentation phenomenon, and its surface resistivity of filming still remains on 2 * 10
-1～2 * 10
2Ω, 0 grade of sticking power, effectiveness of shielding are 68～82dB.Demonstrate good electroconductibility, shielding, package stability and the carbon nanotube dispersing uniformity in urethane.
Advantage of the present invention is: 1. the present invention is incorporated into carbon nanotube in the base polyurethane prepolymer for use as by the method for chemical bonding, the water polyurethane electric conduction paint for preparing carbon nanotubes again by self-emulsification, can prepare a kind of water polyurethane electric conduction paint containing carbon nano-tube, the package stability of this coating and the carbon nanotube dispersing uniformity in resin etc. will be better than traditional physical blending method far away; 2. the water polyurethane electric conduction paint containing carbon nano-tube of the present invention preparation, its volume specific resistance magnitude range of filming is 1 * 10
-5～4 * 10
-4Ω cm, the surface resistivity magnitude range is 1 * 10
-1～2 * 10
2Ω, 0 grade of sticking power, effectiveness of shielding are 70～85dB.The result places back (for example 3 months) for a long time, and this water-borne coatings still keeps stable and do not have generation such as sedimentation phenomenon, and its surface resistivity of filming still remains on 2 * 10
-1～2 * 10
2Ω, 0 grade of sticking power, effectiveness of shielding is 68～82dB, demonstrates good electroconductibility, shielding and package stability; Advantage such as preparation method 3. of the present invention has that simple process is convenient, pollution-free, environmental friendliness, film quality height, input-output ratio height, with low cost and application prospect are extensive; 4. the product that utilizes the present invention to prepare has functions such as conduction and shielding electromagnetic wave, is new generation of green environment-friendly and high-performance Chemicals, can be applicable to fields such as electronic industry, inner wall of oil tank, aerospace, light wave communication, electromagnetic shielding and heating buildings.
Description of drawings
Fig. 1 is the size distribution figure of water polyurethane electric conduction paint containing carbon nano-tube.
Fig. 2 is the projection Electronic Speculum figure of water polyurethane electric conduction paint containing carbon nano-tube.
Embodiment
Embodiment 1
With the 500mg multi-walled carbon nano-tubes adding 150ml vitriol oil and concentrated nitric acid is in the mixed strong acids solution of forming at 3: 1 by volume, and sonic oscillation was handled 4 hours, poured in the deionized water, and leave standstill more than 12 hours, filter and be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching; Under nitrogen protection, the carbon nanotube of the above-mentioned band carboxylic acid of 400mg is placed the excessive thionyl chloride 36h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride; Carbon nanotube with the above-mentioned chloride of 200mg is dispersed in the anhydrous propanone again, under 65 ℃ of conditions, dripping 10ml concentration is the acetone soln of the hexanediamine of 0.01g/ml, the dropping time was not less than 60 minutes, successive reaction 12 hours, centrifuging and be washed to neutrality, 40 ℃ of following vacuum-dryings of temperature obtained containing the carbon nanotube of amino or hydroxyl isoreactivity group more than 12 hours; Again with Toluene-2,4-diisocyanate, 4-vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, dibutyltin dilaurate and N-Methyl pyrrolidone were with 100: 360: 40: the mixed of 2: 400 (weight) is even, be warmed up to 60 ℃ of reactions 8 hours, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer; Again with above-mentioned carbon nanotube, dibutyltin dilaurate and acetone with isocyanate-terminated polyurethane prepolymer, band active group, with 100: 12: 1: the ratio of 100 (weight), stir, temperature is controlled at about 60 ℃, reaction continues 5 hours, add the 4g triethylamine again, temperature is reduced to 45 ℃, reacts 35 minutes.Measure the 350ml deionized water, slowly be added dropwise in the said mixture, keeping the whole dropping time is 45 minutes.After dropwising, continue reaction 30 minutes again.After removing acetone under 35 ℃ of vacuum, obtain the aqueous polyurethane dispersion of carbon nanotubes.At last by a certain percentage at ambient temperature with the mixture of above-mentioned carbon nanotubes aqueous polyurethane dispersion, deionized water, N-Methyl pyrrolidone, dioctyl sulfosuccinate and ethylene glycol monobutyl ether, high-speed stirring 45 minutes, add thickening material then, continue high-speed stirring and made water polyurethane electric conduction paint containing carbon nano-tube in 30 minutes.
The photo in kind of the water polyurethane electric conduction paint of this carbon nanotubes as shown in Figure 1, Fig. 2 and Fig. 3 are respectively its size distribution figure and projection Electronic Speculum figure, and the film performance of water polyurethane electric conduction paint containing carbon nano-tube sees Table 1.
Embodiment 2
Identical with embodiment 1, but with the ratio 100: 12: 1 of carbon nanotube, dibutyltin dilaurate and the acetone of isocyanate-terminated polyurethane prepolymer, band active group: 100 become 100: 20: 1: 100.
Embodiment 3
Identical with embodiment 1, but with the ratio 100: 12: 1 of carbon nanotube, dibutyltin dilaurate and the acetone of isocyanate-terminated polyurethane prepolymer, band active group: 100 become 100: 30: 1: 100.
Embodiment 4
But the ratio 100: 12: 1 with carbon nanotube, dibutyltin dilaurate and the acetone of isocyanate-terminated polyurethane prepolymer, band active group: 100 become 100: 5: 1: 100.
Embodiment 5
But the ratio 100: 12: 1 with carbon nanotube, dibutyltin dilaurate and the acetone of isocyanate-terminated polyurethane prepolymer, band active group: 100 become 100: 2: 1: 100.
Embodiment 6
Identical with embodiment 1, but Toluene-2,4-diisocyanate, 4-vulcabond, polyester polyol, 2, the ratio of 2 '-dimethylol propionic acid, dibutyltin dilaurate and N-Methyl pyrrolidone 100: 360: 40: become 100: 360: 60 at 2: 400: 2: 400.
Embodiment 7
Identical with embodiment 1, but Toluene-2,4-diisocyanate, 4-vulcabond, polyester polyol, 2, the ratio of 2 '-dimethylol propionic acid, dibutyltin dilaurate and N-Methyl pyrrolidone 100: 360: 40: become 100: 360: 20 at 2: 400: 2: 400.
Embodiment 8
Identical with embodiment 1, but hexanediamine becomes 1, the 4-butyleneglycol.
Embodiment 9
Identical with embodiment 1, but Toluene-2,4-diisocyanate, and the 4-vulcabond becomes different Buddhist ketone vulcabond.
Embodiment 10
Identical with embodiment 1, but the dioctyl sulfosuccinate becomes the polyoxyethylene glycol alkyl ester.
Embodiment 11
Identical with embodiment 1, but ethylene glycol monobutyl ether becomes ethylene glycol monomethyl ether.
The coating of the water polyurethane electric conduction paint of the carbon nanotubes that obtains among the embodiment 2-11 and embodiment 1 has similar performance.
Table 1
| Sequence number | It is apparent to film | Surface resistivity | Effectiveness of shielding | Sticking power (level) | Effectiveness of shielding (after 3 months) |
| Embodiment 1 | Glossiness is good, surfacing | 10Ω | 75dB | 0 | 74dB |
| Embodiment 2 | Glossiness is good, surfacing | 5Ω | 81dB | 0 | 80dB |
| Embodiment 3 | Glossiness is good, surfacing | 1Ω | 83dB | 0 | 82dB |
Claims (7)
1. water polyurethane electric conduction paint containing carbon nano-tube, it is characterized in that preparing: at first carbon nanotube is carried out chemically modified by following method, make its surface be with a certain amount of hydroxyl, carboxyl or amido, method by chemical bonding is incorporated into this carbon nanotube in polyester polyol or the isocyanate-terminated base polyurethane prepolymer for use as then, prepare the aqueous polyurethane dispersion of carbon nanotubes again by self-emulsification, last deionized water and the auxiliary agent of adding in the aqueous polyurethane dispersion of carbon nanotubes, high-speed stirring makes water polyurethane electric conduction paint containing carbon nano-tube.
2. the preparation method of a water polyurethane electric conduction paint containing carbon nano-tube as claimed in claim 1 is characterized in that concrete steps are:
(1) be 3 by volume with 100～1000mg multi-walled carbon nano-tubes adding 150ml vitriol oil and concentrated nitric acid: 0.8-3: in the 1.2 mixed strong acids solution of forming, sonic oscillation was handled 3～12 hours, pour in the deionized water, leave standstill more than 12 hours, filter and be washed to neutrality, oven dry obtains the carbon nanotube with carboxyl again;
(2) under nitrogen protection, the carbon nanotube of the above-mentioned band carboxyl of 80～800mg is placed the excessive thionyl chloride 12～72h that refluxes, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 50～500mg is dispersed in the anhydrous propanone, drip several fresh pyridines or triethylamine, under 55-65 ℃ of condition, dropwise Dropwise 5～20ml concentration is the diamine of 0.005～0.025g/ml or the acetone soln of dibasic alcohol, the dropping time was not less than 60 minutes, dropwised successive reaction 4～72 hours, excessive diamine or dibasic alcohol are removed with a large amount of acetone thorough washing, centrifuging, vacuum-drying obtains containing the carbon nanotube of amino or hydroxyl activity group;
(4) with vulcabond, polyester polyol, 2,2 '-dimethylol propionic acid, catalyzer and organic solvent are with 100: 300～400: 20-60: 0.05～5: 300～500 part by weight mixes, be warming up to 55-65 ℃, reacted 6-12 hour, make reaction be tending towards finishing, promptly be able to isocyanate-terminated polyurethane prepolymer;
(5) with above-mentioned isocyanate-terminated polyurethane prepolymer, contain carbon nanotube, catalyzer and the organic solvent of amino or hydroxyl isoreactivity group, mix by part by weight with 100: 1～50: 0.5～2: 50～200, temperature is controlled at 55-65 ℃, reaction continues 4～12 hours, temperature is reduced to 45～55 ℃, add 0.5～5g triethylamine again, reacted 15～60 minutes; Measure 200～500ml deionized water, be added dropwise in the said mixture, the dropping time is 30～60 minutes, and temperature is 45～50 ℃; After dropwising, temperature is 33-36 ℃, continues reaction 25-35 minute again, after vacuum filtration is removed acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes;
(6) at ambient temperature with above-mentioned carbon nanotubes aqueous polyurethane dispersion and deionized water, solubility promoter, wetting agent and membrane-forming agent mixture, stirred 30～60 minutes, add thickening material then, continue to stir 15～60 minutes, promptly make water polyurethane electric conduction paint containing carbon nano-tube.
3. preparation method according to claim 2 is characterized in that described used diamine is quadrol, propylene diamine, 1,4-butanediamine or hexanediamine; Described dibasic alcohol is ethylene glycol, propylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol, 3-chloro-1,2-propylene glycol or decanediol; Said vulcabond is aromatic diisocyanate or aliphatic diisocyanate, and said polyester polyol is the extraordinary polyester polyol or the PCDL of adipate polyester polyvalent alcohol, benzoic anhydride polyester polyol, polycaprolactone polyol, high-molecular-weight poly ester polyol, band side group; Said catalyzer is dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine; Said organic solvent is acetone, butanone, toluene, dimethylbenzene, ethyl acetate, N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide.
4. preparation method according to claim 2 is characterized in that said solubility promoter is N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide.
5. preparation method according to claim 2 is characterized in that said thickening material is Polyacrylic Acid Thickener, cellulose thickener or polyurethane associative thickener.
6. preparation method according to claim 2 is characterized in that said wetting agent is dialkyl group (octyl group, hexyl, butyl) sulfosuccinate, alkyl how sodium sulfonate, Viscotrol C hydrosulfate, sodium laurylsulfonate, sulfuric acid laurel tallow, oleic acid butyl ester hydrosulfate, alkylphenol polyvinyl ether, Voranol EP 2001, polyoxyethylene glycol alkyl ester, polyoxyethylene glycol alkyl aryl ether, acetylene ethylene glycol etc. or polyether modified siloxane.
7. preparation method according to claim 2 is characterized in that said membrane-forming agent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether.
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