CN109384936A - Carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof - Google Patents
Carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 98
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 98
- 239000004814 polyurethane Substances 0.000 title claims abstract description 95
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 95
- 239000003973 paint Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 54
- 238000001962 electrophoresis Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 hydroxyl carbon nanotube Chemical compound 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 63
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- 239000012948 isocyanate Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- 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 18
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 238000004070 electrodeposition Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 9
- 229920005749 polyurethane resin Polymers 0.000 abstract description 7
- 239000004922 lacquer Substances 0.000 abstract description 6
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000009396 hybridization Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 208000005156 Dehydration Diseases 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention proposes that a kind of carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof, belong to carbon nanotube graft modification technical field, it is able to solve carbon nanotube technical problem easy to reunite in aqueous-based polymers matrix, stability and dispersing uniformity of the carbon nanotube in water-base resin are improved, so as to improve the mechanical property and functionality of water-based polyurethane resin.The carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin and is reacted by oligomer polyol, trimethylolpropane, diisocyanate, hydroxyl carbon nanotube, epoxy resin, hydrophilic agent, chain extender and neutralization salt forming agent proportion.The present invention can be applied in the preparation of Polyurethane lacquer, gained paint film has excellent water-fast, acid resistance, electric conductivity and high rigidity, polyurethane electrophoretic paint light richness is greater than 90, hardness is greater than 5H, acid resistance reaches 46h, water resistance is greater than 4608h or more, and the conductivity of paint film can reach 8.29 × 10‑3S/cm。
Description
Technical field
The invention belongs to carbon nanotube graft modification technical fields more particularly to a kind of carbon nanotube to be grafted the poly- ammonia of terminal hydroxy group
Ester electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof.
Background technique
As market constantly promotes polyurethane electrophoretic paint performance indicator, people, which carry out successively in polyurethane, to be crosslinked, is outer
Crosslinking, two-dimensional slice silicate particles are compound, the methods of epoxy resin graft polyurethane resin is carried out it is structurally-modified.However
When demand has the polyurethane electrophoretic coating of conducting function, traditional polyurethane electrophoretic coating is unable to satisfy purposes requirement.
At present it has been reported that carbon nanotube is the particle with excellent electrical and thermal conductivity performance, polymer and carbon nanotube
It is one of research hotspot of materials science field that hybridization compounding, which prepares composite material,.The conductivity of carbon nanotube is up to 1000-
2000S·cm-1, compared with common inorganic filler, carbon nanotube also shows polymer preferably other than energy conducting function
Activeness and quietness effect, be widely used in multiple fields.
Polyurethane/carbon nano-tube composite polyurethane material reported in the literature, usually used is the method reality of physical blending
Existing polyurethane and carbon nano-tube hybridization is compound or carbon nanotube is compound with polyurethane, the existing compound skill that passes through coupling agent
Art does not solve carbon nanotube and disperses scientific and technical problem uneven, easy to reunite in polymer matrix body, to influence carbon nanometer
The dispersing uniformity of pipe in the composite reduces carbon nanotube to compound polyurethane material mechanical property and functional modification
Effect.Also, carbon nanotube is concentrated mainly on the composite modified aspect of solid material to the modification of polymer at present, and for water
Preparing for base nano hybridization polyurethane coating is considerably less, this is mainly also to be that the density of carbon nanotube is higher than water-based polyurethane tree
The density of fat liquor, carbon nanotube is easily settled easily in water-based polyurethane resin, unstable, and carbon nanotube hydridization is not achieved
Effect.
Summary of the invention
The present invention proposes that a kind of carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and its system
Preparation Method, gained polyurethane electrophoresis resin solve carbon nanotube technical problem easy to reunite in aqueous-based polymers matrix, mention
High stability and dispersing uniformity of the carbon nanotube in water-base resin, so as to improve the mechanical property of water-based polyurethane resin
And functionality.
In order to achieve the above object, the present invention provides a kind of carbon nanotubes to be grafted hydroxyl-terminated polyurethane electrophoresis resin, by
The raw material of following weight percent is prepared, and wherein the mass percent of each component raw material is as follows:
Preferably, the oligomer polyol is or mixtures thereof polycarbonate glycol, polycaprolactone diols, institute
The relative molecular weight for stating oligomer polyol is 500-2000.
Preferably, the diisocyanate is or mixtures thereof isophorone diisocyanate, toluene di-isocyanate(TDI).
Preferably, the hydrophilic agent is at least one of N methyldiethanol amine and triethanolamine；The asphalt mixtures modified by epoxy resin
Rouge is E-44 epoxy resin；The chain extender is neopentyl glycol；The neutralization salt forming agent is lactic acid, oxalic acid or tartaric acid.
The carbon nanotube grafting hydroxyl-terminated polyurethane electricity that the present invention also provides a kind of as described in any of the above-described technical solution
The preparation method of swimming resin, comprising the following steps:
Hydroxyl carbon nanotube is dried in vacuo at 100-120 DEG C, is then mixed with toluene diisocyanate, in 60-80
Ultrasonic reaction at DEG C, then high speed centrifugation, obtains the Activated Carbon Nanotubes of oil-soluble isocyanato reaction modification, its is molten
Solution is uniformly mixed in isophorone diisocyanate, obtains the carbon nanotube and isophorone diisocyanate of isocyano modification
The mixture of ester；
Oligomer polyol and trimethylolpropane are carried out dehydrating, the carbon nanometer of isocyano modification is then added
Polymerization reaction occurs for pipe and the mixture of isophorone diisocyanate；
In the presence of solvent, hydrophilic agent is added in Xiang Shangshu polymerization reaction system to be reacted, reaction temperature 30-50
DEG C, reaction time 2-4h；
In the presence of solvent, chain extender is continuously added in Xiang Shangshu reaction system and epoxy resin is reacted, reaction temperature
Degree is 70-90 DEG C, reaction time 2-4h；
It is continuously added into above-mentioned reaction system and neutralizes salt forming agent reaction, reaction temperature is 10-40 DEG C, and the reaction time is
0.5-2h obtains carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin.
Preferably, dehydration temperature is 100-120 DEG C, dehydration treatment time 1.0-1.5h；Polymeric reaction temperature
It is 50-70 DEG C, polymerization reaction time 2-3h.
Preferably, the solvent is Isosorbide-5-Nitrae-dioxane, N methyl pyrrolidone, butyl glycol ether and N, N- dimethyl
At least one of formamide.
Organotin or Organic leadP class catalyst is added when preferably, hydrophilic agent reaction being added into polymerization reaction system.
The present invention also provides a kind of cathode polyurethane electrophoretic paints, are prepared by the raw material of following mass percent,
The mass percent of middle each component raw material is as follows:
Carbon nanotube as described in the above technical scheme is grafted hydroxyl-terminated polyurethane electrophoresis resin: 24.5%-26.4%
Cationic water dispersible end capping type isocyanates: 6.6%-7.0%
Propylene glycol phenylate: 0.73%-0.74%
Deionized water: 65.9%-68.1%.
Preferably, such as above-mentioned technical side is added in cationic water dispersible end capping type isocyanates and propylene glycol phenylate
Carbon nanotube described in case is grafted in hydroxyl-terminated polyurethane electrophoresis resin, is mixed, and after deionized water emulsification shearing, is obtained
Polyurethane electrocoating paint, forms a film through electrophoresis coating technique, baking, and secondary cross-linking baking film forming occurs.
Compared with prior art, the advantages and positive effects of the present invention are:
1, the present invention uses multistep step-reaction polymerization when preparing carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin,
It is not related to small molecule such as waste water, exhaust gas in reaction to generate, safety and environmental protection is environmental-friendly；
2, multiple hydroxy functional groups in carbon nanotube are prepared into the modified work of isocyano with di-isocyanate reaction
Property carbon nanotube, Activated Carbon Nanotubes and isophorone mix to form the mixing isocyanate mixture of nano hybridization；
3, using home position polymerization reaction, carbon nanotube is grafted on the molecular backbone of polyurethane, makes polyurethane macromolecular
It completes to coat the macromolecular chain of carbon nanotube after removing carbon nanotube, reduces the sedimentation that carbon nanotube self assembly aggregation occurs
Phenomenon improves the stability of polyurethane/carbon nano-tube composite electrodeposition resin, solves carbon nanotube and settle in water-based resin
Common technology problem, can give full play to the nano effect of carbon nanotube, improve the comprehensive performance of polyurethane electrocoating paint；
4, the hydroxyl-terminated polyurethane nanometer being grafted using cationic water dispersible end capping type isocyanates and carbon nanotube
Hydridization electrodeposition resin can exist with arbitrary proportion mixed stability, and nothing settles out phenomenon, gained electrophoretic paint after emulsifying in water
Film under high-temperature baking blocked isocyanate can high temperature unlock isocyano (- NCO) functional group, in resin hydroxyl send out
Biochemical cross-linking reaction improves the chemical corrosion resistance of Polyurethane lacquer；
5, the paint film that is formed by curing of the present invention has excellent water-fast, acid resistance, electric conductivity and high rigidity, polyurethane
Electrophoretic paint light richness is greater than 90, and hardness is greater than 5H, and acid resistance reaches 46h, and water resistance is greater than 4608h or more, and paint film is led
Electric rate can reach 8.29 × 10-3S/cm。
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The embodiment of the invention provides a kind of carbon nanotubes to be grafted hydroxyl-terminated polyurethane electrophoresis resin, by following quality percentage
The raw material of ratio is prepared, and wherein the weight percent of each component raw material is as follows:
Carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin provided in an embodiment of the present invention utilizes toluene di-isocyanate(TDI)
Reaction modifying is carried out to hydroxyl carbon nanotube, the carbon nanotube of isocyanate groups reaction modification is made.Since the carbon of preparation is received
There are reactive isocyanate-reactive functional groups on the surface of mitron, therefore can be led to carbon nanotube using the method for in-situ polymerization
Chemical reaction is crossed to be connected chemically with the molecular backbone of polyurethane, formed carbon nanotube be grafted the new polyurethane of macromolecular main chain/
Carbon nanotube composite electrodeposition resin preferably solves the carbon nanotube technical problem easily settled in water-based resin, can be effective
Improve carbon nano-tube hybridization electrocoating paint stability and the subsequent water-based polyurethane paint film being prepared it is comprehensive
Can, such as hardness, wearability, chemicals-resistant, water resistance acid resistance, mechanical property, while it is good to assign polyurethane electrocoating paint
Electric conductivity and antistatic property.
In an alternative embodiment, the oligomer polyol be polycarbonate glycol, polycaprolactone diols or its
Mixture, the relative molecular weight of the oligomer polyol are 500-2000, and preferably relative molecular weight is 1000.In an optional reality
It applies in example, the diisocyanate is or mixtures thereof isophorone diisocyanate, toluene di-isocyanate(TDI).In an optional reality
It applies in example, the hydrophilic agent is at least one of N methyldiethanol amine and triethanolamine；The epoxy resin is E-44 ring
Oxygen resin；The chain extender is neopentyl glycol；The neutralization salt forming agent is lactic acid, oxalic acid or tartaric acid.
Above-described embodiment to selected oligomer polyol, diisocyanate, hydrophilic agent, chain extender, epoxy resin and
It neutralizes salt forming agent and has carried out specific restriction, limiting in this way is in order to ensure reacting acquired product to be expected and having desirability
The product of energy.It is understood that it is, in principle, that those skilled in the art can be to the substance foundation cited by above-described embodiment
Common sense is rationally replaced, but is found after multi-party verification, and replaced combination can not be obtained with the application
The performance of product and preparation-obtained electrophoretic paint compares favourably.
The carbon nanotube that the present invention also provides a kind of as described in above-described embodiment is grafted hydroxyl-terminated polyurethane electrophoresis resin
Preparation method, comprising the following steps:
S1: hydroxyl carbon nanotube is dried in vacuo at 100-120 DEG C, is then mixed with toluene diisocyanate, in 60-
Ultrasonic reaction at 80 DEG C, then high speed centrifugation, obtains the Activated Carbon Nanotubes of oil-soluble isocyanato reaction modification, by it
It is dissolved in isophorone diisocyanate and is uniformly mixed, obtain two isocyanide of carbon nanotube and isophorone of isocyano modification
The mixture of acid esters；
In this step, first hydroxyl carbon nanotube is dried, main purpose is to remove the absorption water of hydrogen bonding effect,
In order to dry abundant, drying time can be 2-3h, can specifically adjust according to the actual situation.Then toluene di-isocyanate(TDI) pair is utilized
Hydroxyl carbon nanotube carries out reaction modifying, and the carbon nanotube of isocyanate groups reaction modification is made.Due to the carbon nanometer of preparation
There are reactive isocyanate-reactive functional groups on the surface of pipe, therefore can be by passing through of carbon nanotube using in-situ polymerization
It learns reaction and the molecular backbone of polyurethane is connected chemically, the new polyurethane/carbon for forming carbon nanotube grafting macromolecular main chain is received
Mitron composite electrodeposition resin preferably solves carbon nanotube technical problem easily settled in water-based polyurethane resin, from
And improve the stability of carbon nano-tube hybridization electrocoating paint.
S2: oligomer polyol and trimethylolpropane are carried out dehydrating, and the carbon of isocyano modification is then added
Polymerization reaction occurs for nanotube and the mixture of isophorone diisocyanate；
In this step, hydroxy-terminated polymer acts on the hydrone in easily absorption air due to hydrogen bonding, these hydrones must
Vacuum it must deviate under the first step process high temperature, otherwise a small amount of hydrone will make polyol blends and diisocyanate
The reaction of mixture causes preparation to fail due to crosslinking reaction, can not carry out the gradually polymerization chain extending reaction of next step.
In order to ensure oligomer polyol and trimethylolpropane dehydration sufficiently, in a preferred embodiment, dehydration temperature
It is 100-120 DEG C, dehydration treatment time 1.0-1.5h；Polymeric reaction temperature is 50-70 DEG C, polymerization reaction time 2-3h.
It can according to the actual situation within the above range or root for restriction those skilled in the art of dehydration, polymeric reaction temperature and time
Floating adjustment is carried out according to above range, is sufficiently carried out as long as ensuring to be dehydrated with polymerization reaction.
S3: being added hydrophilic agent in the presence of solvent, in Xiang Shangshu polymerization reaction system and reacted, reaction temperature 30-
50 DEG C, reaction time 2-4h；
In this step, hydrophilic chain extender is added in addition to can gradually polymerize chain extending reaction with the performed polymer generation of S2 step preparation
Outside, hydrophilic functional groups " tertiary carbon " atom also is introduced to polyurethane macromolecular main chain, it is ensured that the carbon nano-tube hybridization of synthesis polymerize
Object can disperse self-emulsifying in water.It is understood that the restriction sheet of reaction temperature and time for above-mentioned reaction system
Field technical staff can carry out floating adjustment within the above range or according to above range according to the actual situation, as long as ensuring to react
Sufficiently carry out.In addition, organotin can also be added in above-mentioned reaction system or Organic leadP class is urged in an alternative embodiment
Agent can ensure to react in this way and react the synthetic that design is successfully prepared at low temperature.
S4: in solvent under, continuously adding chain extender and epoxy resin reacted in Xiang Shangshu reaction system, reaction temperature
Degree is 70-90 DEG C, reaction time 2-4h；
In this step, hydrophilic chain extender is gradually polymerize chain extending reaction at low temperature, completes the chain extension effect of macromolecular,
Make it possible that polymer is scattered in water due to introducing hydrophilic functional groups on macromolecular chain simultaneously.Epoxy resin equally plays
The effect of chain extension or grafting, the presence of epoxy molecule structure improve the resistance to acid and alkali and water resistance of polyurethane resin.It needs
It is bright, specific restriction has been carried out for chain extender and epoxy resin in this step, wherein and chain extender is neopentyl glycol,
Epoxy resin is E-44 epoxy resin, can ensure that chain extender neopentyl glycol can play the flexibility for improving Polyurethane lacquer in this way
Effect.
It is continuously added in S5: Xiang Shangshu reaction system and neutralizes salt forming agent reaction, reaction temperature is 10-40 DEG C, the reaction time
For 0.5-2h, carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin is obtained.
In this step, the purpose that ackd salt agent is added is Hydrogen Proton and tertiary N atom acid-base neutralization making poly- ammonia at salt
Ester resin shows stronger hydrophilic ability, using less hydrophilic agent it is ensured that polyurethane resin adequately emulsifies in water
Dispersion.It is understood that restriction those skilled in the art of reaction temperature and time for above-mentioned reaction system can basis
Actual conditions carry out floating adjustment within the above range or according to above range, as long as ensuring to react sufficiently progress.In addition,
In above-mentioned steps, the solvent is Isosorbide-5-Nitrae-dioxane, N methyl pyrrolidone, butyl glycol ether and N, N- dimethyl formyl
At least one of amine, these solvents are easy and water phase is molten, can preferably apply in this system, it is contemplated that potentially to people
Health influence, Isosorbide-5-Nitrae-dioxane is more satisfactory.The embodiment of the invention also provides a kind of electrophoretic paint, by with
The raw material of lower weight percent is prepared, and wherein the mass percent of each component raw material is as follows: carbon nanotube is grafted terminal hydroxy group
Polyurethane electrophoresis resin: 24.5%-26.4%, cationic water dispersible end capping type isocyanates: 6.6%-7.0%, the third two
Alcohol phenylate: 0.73%-0.74%, deionized water: 65.9%-68.1%.
In an alternative embodiment, cationic water dispersible end capping type isocyanates and propylene glycol phenylate are added as above
It states in the grafting hydroxyl-terminated polyurethane electrophoresis resin of carbon nanotube described in technical solution, is mixed, cut in deionized water emulsification
After cutting, polyurethane electrocoating paint is obtained, is formed a film through electrophoresis coating technique, toasted, secondary cross-linking baking film forming occurs.
Cathode polyurethane electrophoretic paint provided by the above embodiment and preparation method thereof uses water dispersible end capping type isocyanic acid
Ester and the hydroxyl-terminated polyurethane nano hybridization electrodeposition resin of carbon nanotube grafting can exist with arbitrary proportion mixed stability, in water
Without settling out phenomenon after middle emulsification, gained electrophoretic paint at high temperature blocked isocyanate can high temperature unlock isocyano-
NCO functional group occurs chemical crosslink reaction with the hydroxyl in resin, is effectively improved the chemical corrosion resistance of Polyurethane lacquer.Institute
Paint film has excellent water-fast, acid resistance, electric conductivity and high rigidity, polyurethane electrophoretic paint light richness is greater than 90, firmly
Degree is greater than 5H, and acid resistance reaches 46h, and water resistance is greater than 4608h or more, and the conductivity of paint film can reach 8.29 × 10-3S/cm。
It is understood that core ideas according to the present invention, the mode realized not only can be heavy based on cationic electricity
Product coating preparation cathode polyurethane electrophoretic paint paint film can also prepare anode polyurethane electrophoretic paint based on anionic electrocoating paint
Paint film.Specifically, when preparing anionic electrocoating paint, parent used when only need to will prepare cationic electro-dipcoat paint
Aqua is replaced in dihydromethyl propionic acid and dimethylolpropionic acid by least one of N methyldiethanol amine and triethanolamine
At least one, salt forming agent will be neutralized by lactic acid, oxalic acid or tartaric acid and replace with triethylamine or ammonium hydroxide, while into one
When step prepares anode polyurethane electrophoretic paint paint film, cationic used when also only need to will prepare cathode polyurethane electrophoretic paint paint film
Water dispersible end capping type isocyanates replaces with anionic water dispersible end capping type isocyanates, before remaining condition is constant
It puts, anode polyurethane electrophoretic paint paint film can be prepared.The anode polyurethane electrophoretic paint paint being prepared based on this method
Film production technique is easy to control, reacting balance, is mainly used for the electrophoretic painting of aluminum profile.
The grafting hydroxyl-terminated polyurethane electrophoresis of carbon nanotube provided by the embodiment of the present invention is introduced in detail in order to become apparent from
Resin, cathode polyurethane electrophoretic paint and preparation method thereof, are described below in conjunction with specific embodiment.
Embodiment 1
Polycarbonate glycol 11.1g and trimethylolpropane 1.0g are taken, is carried out dehydrating 1h at 90 DEG C；Take containing
The carbon nanotube of 0.3g isocyano modification and the mixture 44.7g of isophorone diisocyanate are added to the reaction of previous step
In, 2h is reacted at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 13.5g N methyldiethanol amine is added, 40
2h is reacted at DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 4.8g epoxy resin and 9.8g neopentyl glycol is added, at 80 DEG C
Chain extending reaction 2h；30 DEG C are finally cooled to, 6.8g glacial acetic acid, 6g n-butanol and 12g butyl glycol ether neutralization reaction 1h is added, obtains
Hydroxyl-terminated polyurethane electrophoresis resin is grafted to carbon nanotube.
The above-mentioned carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin of 48g is taken again, and 11.1g cationic water is added thereto
After dispersible blocked isocyanate and 1.4g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming, in 80 DEG C of baking ovens
Then middle baking 30min is warming up to 140 DEG C of holding 1h, secondary cross-linking occurs to get electrophoretic paint is arrived.
Embodiment 2
Polycarbonate glycol 13.9g and trimethylolpropane 1.2g are taken, is carried out dehydrating 1h at 90 DEG C；Take containing
The carbon nanotube of 0.75g isocyano modification and the mixture 55.9g of isophorone diisocyanate are added to the anti-of previous step
Ying Zhong reacts 2h at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 16.9g N methyldiethanol amine is added,
2h is reacted at 40 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 6.1g epoxy resin and 12.3g neopentyl glycol is added,
80 DEG C of chain extending reaction 2h；30 DEG C are finally cooled to, is added in 8.5g glacial acetic acid, 7.5g n-butanol and 15g butyl glycol ether and anti-
1h is answered, carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin is obtained.
The above-mentioned carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin of 60g is taken again, and 14.13g cationic is added thereto
After water dispersible end capping type isocyanates and 1.8g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming is dried at 80 DEG C
30min is toasted in case, is then warming up to 140 DEG C of holding 1h, and secondary cross-linking occurs to get electrophoretic paint is arrived.
Embodiment 3
Polycarbonate glycol 16.70g and trimethylolpropane 1.5g are taken, is carried out dehydrating 1h at 90 DEG C；Take containing
The carbon nanotube of 1.4g isocyano modification and the mixture 67.1g isophorone diisocyanate of isophorone diisocyanate
In, then mixture entered into the reaction of previous step, 2h is reacted at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane,
20.2gN- methyl diethanolamine is added, reacts 2h at 40 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 7.3g is added
Epoxy resin and 14.8g neopentyl glycol, in 80 DEG C of chain extending reaction 2h；30 DEG C are finally cooled to, 10.2g glacial acetic acid, 9g is being added just
Butanol and 18g butyl glycol ether neutralization reaction 1h obtain carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin.
The above-mentioned carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin of 72g is taken again, and 16.6g cationic water is added thereto
After dispersible blocked isocyanate and 2.2g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming, in 80 DEG C of baking ovens
Then middle baking 30min is warming up to 140 DEG C of holding 1h, secondary cross-linking occurs to get electrophoretic paint is arrived.
Embodiment 4
Polycarbonate glycol 17.6g and trimethylolpropane 1.6g are taken, is carried out dehydrating 1h at 90 DEG C；Take containing
The carbon nanotube of 1.9g isocyano modification and the mixture 70.8g of isophorone diisocyanate are added to the reaction of previous step
In, 2h is reacted at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 21.4gN- methyl diethanolamine is added, at 40 DEG C
Lower reaction 2h；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 7.714g epoxy resin and 15.6g neopentyl glycol is added, 80
DEG C chain extending reaction 2h；30 DEG C are finally cooled to, 10.8g glacial acetic acid, 9.5g n-butanol and 19g butyl glycol ether neutralization reaction is added
1h obtains carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin.
The above-mentioned carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin of 76g is taken again, and thereto plus 17.6g cationic water can
After dispersion blocked isocyanate and 2.3g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming, in 80 DEG C of baking ovens
30min is toasted, 140 DEG C of holding 1h are then warming up to, secondary cross-linking occurs to get electrophoretic paint is arrived.
Embodiment 5
Polycarbonate glycol 18.6g and trimethylolpropane 1.7g are taken, is carried out dehydrating 1h at 90 DEG C；Take containing
The carbon nanotube of 2.5g isocyano modification and the mixture 74.5g of isophorone diisocyanate are added to the reaction of previous step
In, 2h is reacted at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 22.5gN- methyl diethanolamine is added, at 40 DEG C
Lower reaction 2h；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 8.1g epoxy resin and 16.4g neopentyl glycol is added, at 80 DEG C
Chain extending reaction 2h；30 DEG C are finally cooled to, 11.3g glacial acetic acid, 10g n-butanol and 20g butyl glycol ether neutralization reaction 1h is added,
Obtain carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin.
The above-mentioned carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin of 80g is taken again, and 18.5g cationic water is added thereto
After dispersible blocked isocyanate and 2.4g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming, in 80 DEG C of baking ovens
Then middle baking 30min is warming up to 140 DEG C of holding 1h, secondary cross-linking occurs to get electrophoretic paint is arrived.
Comparative example 1
Polycarbonate glycol 9.3g and trimethylolpropane 0.83g are taken, is carried out dehydrating 1h at 90 DEG C；It adds
37.2g isophorone diisocyanate.2h is reacted at 80 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, 11.2g is added
N methyldiethanol amine reacts 2h at 40 DEG C；Again in the presence of solvent Isosorbide-5-Nitrae-dioxane, be added 4.1g epoxy resin and
8.2g neopentyl glycol, in 80 DEG C of chain extending reaction 2h；30 DEG C are finally cooled to, 5.6g lactic acid, 5g n-butanol and 10g ethylene glycol is added
Monomethyl ether neutralization reaction 1h, obtains hydroxyl-terminated polyurethane electrophoresis resin.
The above-mentioned hydroxyl-terminated polyurethane electrophoresis resin of 40g is taken again, and 9.42g cationic water dispersible end capping type is added thereto
After isocyanates and 1.2g propylene glycol phenylate emulsify shearing in water, electrodeposited film forming toasts 30min in 80 DEG C of baking ovens,
Then 140 DEG C of holding 1h are warming up to, secondary cross-linking occurs to get electrophoretic paint is arrived.
Performance test
Above-described embodiment 1-5 and 1 gained electrophoretic paint of comparative example are tested for the property, test method is as follows, the results are shown in Table
1。
Glossiness: according to GB/T9754-2007 using the portable mirror luster measurement examination gloss of film degree of WGG.
Pencil hardness: according to the GB/T6739-2006 hardness of measuring pencil durometer paint film.
Water resistance: the water resistance of detection paint film is carried out referring to the test method of 4761-2014 " aqueous polyurethane coatings ".
Acid resistance: according to GB/T9274-1988, paint film is impregnated in the hydrochloric acid solution that mass fraction is 5%, until paint
There is the sign taking-up that bleaches in film surface, and record paint film bleaches the time used.
Conductivity: with the electric conductivity of U.S. Lan Shi Ransburg, 76652-03 conductivity meter test paint film.
The performance of 1 gained electrophoretic paint of 1 embodiment 1-5 of table and comparative example compares
From the data in table 1, it can be seen that in the formula of the carbon nano-tube hybridization polyurethane electrodeposition resin of the application protection, carbon nanometer
Compared with 1 blank formula of comparative example, the pencil hardness of Polyurethane lacquer increases to 5H by 4H for presence of the pipe in polyurethane matrix,
Measuring this key index of cationic electro-dipcoat paint acid resistance also increases to 46h, the coating of paint film by the 8h of blank sample
It can be greatly improved.The most valuable, carbon nanotube grafts on the molecular backbone of polyurethane, also imparts Polyurethane lacquer
Conductive functionality, the nano effect of carbon nanotube greatly improve the interior quality of cathode polyurethane electrophoretic paint paint film, are promoted
The market innovation power of polyurethane electrocoating paint.
Claims (10)
1. a kind of carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, which is characterized in that by the raw material of following mass percent
It is prepared, wherein the weight percent of each component raw material is as follows:
2. carbon nanotube according to claim 1 is grafted hydroxyl-terminated polyurethane electrophoresis resin, which is characterized in that described oligomeric
Object polyalcohol is or mixtures thereof polycarbonate glycol, polycaprolactone diols, the average molecular of the oligomer polyol
Amount is 500-2000.
3. carbon nanotube according to claim 1 is grafted hydroxyl-terminated polyurethane electrophoresis resin, which is characterized in that described two is different
Cyanate is or mixtures thereof isophorone diisocyanate, toluene di-isocyanate(TDI).
4. carbon nanotube according to claim 1 is grafted hydroxyl-terminated polyurethane electrophoresis resin, which is characterized in that described hydrophilic
Agent is at least one of N methyldiethanol amine and triethanolamine；The epoxy resin is E-44 epoxy resin；The chain extension
Agent is neopentyl glycol；The neutralization salt forming agent is lactic acid, oxalic acid or tartaric acid.
5. the preparation method of carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin according to claim 1-4,
Characterized by comprising the following steps:
Hydroxyl carbon nanotube is dried in vacuo at 100-120 DEG C, is then mixed with toluene diisocyanate, at 60-80 DEG C
Ultrasonic reaction, then high speed centrifugation, obtains the Activated Carbon Nanotubes of oil-soluble isocyanato reaction modification, is dissolved in
It is uniformly mixed in isophorone diisocyanate, obtains the carbon nanotube and isophorone diisocyanate of isocyano modification
Mixture；
Oligomer polyol and trimethylolpropane are carried out dehydrating, then be added isocyano modification carbon nanotube and
Polymerization reaction occurs for the mixture of isophorone diisocyanate；
In the presence of solvent, hydrophilic agent is added in Xiang Shangshu polymerization reaction system to be reacted, reaction temperature is 30-50 DEG C, instead
It is 2-4h between seasonable；
In the presence of solvent, chain extender being continuously added in Xiang Shangshu reaction system and epoxy resin being reacted, reaction temperature is
70-90 DEG C, reaction time 2-4h；
It is continuously added into above-mentioned reaction system and neutralizes salt forming agent reaction, reaction temperature is 10-40 DEG C, reaction time 0.5-
2h obtains carbon nanotube grafting hydroxyl-terminated polyurethane electrophoresis resin.
6. preparation method according to claim 5, which is characterized in that dehydration temperature is 100-120 DEG C, dehydration
Time is 1.0-1.5h；Polymeric reaction temperature is 50-70 DEG C, polymerization reaction time 2-3h.
7. preparation method according to claim 5, which is characterized in that the solvent is Isosorbide-5-Nitrae-dioxane, N methylpyrrole
At least one of alkanone, butyl glycol ether and N,N-dimethylformamide.
8. preparation method according to claim 5, which is characterized in that when hydrophilic agent reaction being added into polymerization reaction system
Organotin or Organic leadP class catalyst is added.
9. a kind of cathode polyurethane electrophoretic paint, which is characterized in that be prepared by the raw material of following mass percent, wherein each group
Divide the mass percent of raw material as follows:
Carbon nanotube as described in claim 1 is grafted hydroxyl-terminated polyurethane electrophoresis resin: 24.5%-26.4% cationic water
Dispersible blocked isocyanate: 6.6%-7.0%
Propylene glycol phenylate: 0.73%-0.74%
Deionized water: 65.9%-68.1%.
10. the preparation method of cathode polyurethane electrophoretic paint according to claim 9, which is characterized in that by cationic water
Dispersible blocked isocyanate and propylene glycol phenylate are added carbon nanotube as described in claim 1 and are grafted hydroxyl-terminated polyurethane
It in electrophoresis resin, is mixed, after deionized water emulsification shearing, polyurethane electrocoating paint is obtained, through electrophoresis coating technique
Film forming, baking occur secondary cross-linking, obtain electrophoretic paint.
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