CN116715953B - Antistatic self-repairing polyurethane material suitable for marine environment and preparation method and application thereof - Google Patents
Antistatic self-repairing polyurethane material suitable for marine environment and preparation method and application thereof Download PDFInfo
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- CN116715953B CN116715953B CN202311005873.7A CN202311005873A CN116715953B CN 116715953 B CN116715953 B CN 116715953B CN 202311005873 A CN202311005873 A CN 202311005873A CN 116715953 B CN116715953 B CN 116715953B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 109
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 32
- 239000004925 Acrylic resin Substances 0.000 claims description 28
- 229920000178 Acrylic resin Polymers 0.000 claims description 28
- -1 2, 4-dihydroxyphenethylamine hydrochloride Chemical compound 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 11
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical compound [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 claims description 11
- 229960004484 carbachol Drugs 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 claims description 9
- 229960004266 acetylcholine chloride Drugs 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 14
- 239000013535 sea water Substances 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 238000012661 block copolymerization Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- PBGQLEYZVZPUGG-UHFFFAOYSA-N prop-2-eneperoxoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OOC(=O)C=C PBGQLEYZVZPUGG-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000002216 antistatic agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229960001231 choline Drugs 0.000 description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- FMYZXPWRXLBAOV-UHFFFAOYSA-N 2-hydroxyethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCO FMYZXPWRXLBAOV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JRLZYKZRJOLHIJ-UHFFFAOYSA-N 2-prop-1-enoxyoxolane Chemical group O1C(CCC1)OC=CC JRLZYKZRJOLHIJ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an antistatic self-repairing polyurethane material suitable for marine environment, a preparation method and application thereof. The hydroxyl acrylate and polyurethane are subjected to block copolymerization to form a stable and controllable crosslinking structure, a large number of hydrogen bonds and ionic bonds contained in the acrylic acid-hydroxyl acrylate copolymerization segment are utilized to carry out double bonding with an ionic conductive agent, conductive ions are introduced, and the resistivity of the material is reduced to 10 7 Omega-m class; the capping agent containing the ortho-phenolic hydroxyl groups is used for capping, and the self-repairing capability of the material is endowed by utilizing a great amount of metal complex bonds existing in seawater, so that the self-repairing capability of the material in a marine environment is enhanced. The material has excellent mechanical, self-repairing and antistatic properties, and has good application prospects in the fields of ocean engineering, submarine tunnels, oil gas transportation, submarine cables and submarine pipes and the like.
Description
Technical Field
The invention relates to an antistatic self-repairing polyurethane material suitable for marine environment, and a preparation method and application thereof, and belongs to the technical field of new materials.
Background
Polyurethane materials have wide applications in numerous industrial fields, including ocean engineering, navigation, ocean resource development, and the like. However, because the traditional polyurethane material is an insulator, static electricity is easy to generate, flammable substances such as oil gas and the like cannot be conveyed as a pipeline, the application range of the polyurethane material is limited, and meanwhile, because the external conditions in the marine environment are complex, the polyurethane material is easy to damage in the marine environment, and the performance and the service life of the material are further influenced. Therefore, a new antistatic self-repairing polyurethane material is needed, which can effectively inhibit static accumulation in marine environment and has self-repairing capability so as to improve the service life and performance of the material.
At present, some researches on antistatic and self-repairing polyurethane materials are carried out, wherein the antistatic performance is mainly realized by adding conductive filler or static eliminator into the polyurethane materials, or the self-healing of the materials is realized by self-repairing microcapsules and nano-particles. However, these methods have some drawbacks. First, the addition of fillers may lead to a decrease in the mechanical properties of the material, thereby limiting its practical use. Second, these materials are subject to interference from factors such as salt, limiting their use in marine environments. Meanwhile, polyurethane materials capable of realizing self-repairing and antistatic capabilities at the same time are recently reported.
For example, patent CN111073498A discloses a UV-cured self-repairing antistatic coating, which uses nano conductive particles to disperse in resin to obtain antistatic capability, uses modified polythiophene as self-repairing crosslinking agent, and is miscible with other resin components, and forms a crosslinked network structure with other UV-cured components during curing, so that the attenuation or failure of antistatic function caused by migration and abrasion to the surface of the coating or migration and aggregation in the interior during long-term use is avoided; by being matched with the self-repairing component, the wear-resistant composite material has good wear resistance, bending crack resistance, scratch resistance and tensile property. However, the resin cannot be molded independently, needs to be compounded with other resins, and has the problems that the self-repairing capability and the antistatic capability are reduced in actual use, and the use requirement is difficult to meet. Patent CN107556920a discloses a self-repairing antistatic coating, in which a resin prepolymer is encapsulated into self-repairing microcapsules by using an emulsifier, and the self-repairing capability of the coating is obtained by adding the microcapsules into the coating resin; meanwhile, the antistatic powder is added, so that the paint has antistatic capability, and has a certain self-repairing effect on the basis of a good antistatic effect, and when the paint generates microcracks, the paint is actively repaired, so that the service life of the antistatic paint can be greatly prolonged, and the paint has a great application prospect. However, the self-repairing and antistatic properties are obtained by physical blending, so that the uniformity of the material is reduced, the mechanical property is reduced, and the prepared material cannot be applied to a scene with high requirements on the mechanical property.
Therefore, the invention aims to provide an antistatic self-repairing polyurethane material suitable for marine environment and a preparation method thereof, and the antistatic self-repairing polyurethane material has the antistatic property and the self-repairing function by reasonably selecting antistatic agents and self-repairing components and performing special treatment, so that the service life and the stability of the polyurethane material in the marine environment are improved.
Disclosure of Invention
The invention aims to provide an antistatic self-repairing polyurethane material suitable for marine environment, so as to improve the safety and service life of the polyurethane material and meet the requirements of modern engineering application.
Meanwhile, the invention provides a preparation method of the antistatic self-repairing polyurethane material suitable for marine environment, which is characterized in that hydroxyl acrylate and polyurethane are subjected to block copolymerization to form a stable and controllable crosslinking structure, a large number of hydrogen bonds and ionic bonds contained in acrylic acid-hydroxyl acrylate copolymerization segments are utilized to carry out double bonding with an ionic conductive agent, conductive ions are introduced, and the material resistivity is reduced to 10 7 Omega-m class; using compounds containing ortho-phenolic hydroxyl groupsThe end capping agent is used for end capping, a great amount of metal complex bonds existing in seawater are utilized to endow the material with self-repairing capability, and the self-repairing capability of the material in a marine environment is enhanced.
Meanwhile, the invention provides application of the antistatic self-repairing polyurethane material suitable for the marine environment in marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
In order to solve the technical problems, the invention adopts the following technical scheme:
an antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 80-120 parts by weight of polyurethane acrylic resin prepolymer, 10-20 parts by weight of end capping agent, 20-35 parts by weight of ion conducting agent, 50-80 parts by weight of solvent and 0.2-0.5 part by weight of AIBN initiator.
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following steps:
(1) Adding 80-120 parts by weight of polyurethane acrylic resin prepolymer and 20-35 parts by weight of ionic conductive agent into a reaction kettle, heating to 80-100 ℃, and stirring for 1-3 hours;
(2) Adding 10-20 parts by weight of a blocking agent into the product of the step (1), and stirring for 2-3 hours at 60-80 ℃ under the protection of nitrogen to obtain a solution;
(3) And (3) pouring the solution obtained in the step (2) into a mold, and drying for 60-80 hours at 160-180 ℃.
The preparation method of the polyurethane acrylic resin prepolymer comprises the following steps:
(01) Adding 75-110 parts by weight of hexamethylene diisocyanate, 50-70 parts by weight of polyethylene glycol with Mn of 1000-3000 and 5-20 parts by weight of acrylic acid into a reaction kettle, adding 0.1-0.3 part by weight of dibutyl tin laurate catalyst, and reacting for 30-50 minutes at 60-80 ℃ under the protection of nitrogen to obtain a first reaction solution;
(02) Adding 30-50 parts by weight of hydroxyl acrylate and 0.2-0.5 part by weight of AIBN initiator into the first reaction liquid in the step (01), reacting for 60-120 minutes at 60-80 ℃ under the protection of nitrogen, and controlling the average polymerization degree of acrylic monomers in the polymer to be 200-400 to obtain a second reaction liquid;
the acrylic monomer is obtained from acrylic acid in the step 01 and hydroxy acrylate in the step 02 and other raw materials under specific reaction time and temperature, the average polymerization degree of the polymerization reaction is not a definite value, and the molecular chain of the acrylic monomer obtained after the polymerization is long or short, so the average polymerization degree is a numerical range;
(03) Mixing 10-15 parts by weight of hydroxyl acrylate, 2-4 parts by weight of pentaerythritol triacrylate, 10-15 parts by weight of polyether polyol and 50-80 parts by weight of solvent, dropwise adding the mixture into the reaction liquid II in the step (02) at the speed of 10-20 parts by weight/min, and reacting for 150-180 minutes at the temperature of 80-100 ℃ under the protection of nitrogen to obtain a polyurethane acrylic resin prepolymer;
the polyester polyol generally refers to a polyester polyol obtained by polycondensation of a dicarboxylic acid with a diol or the like. In a broad sense, polyols containing ester groups (COO) or carbonate groups (OCOO). Polyether polyols for polyurethane polymerization are numerous and are used in various industries, and in particular, the polyether polyols may be one or more combinations of polyoxypropylene diols, polyoxypropylene triols, polytetrahydrofuran diols, tetrahydrofuran-oxypropylene copolyols.
The hydroxy acrylate is one or more of hydroxy ethyl methacrylate, hydroxy propyl methacrylate and hydroxy ethyl ethylacrylate.
The ionic conductive agent is one or a combination of a plurality of choline chloride, acetylcholine chloride and carbachol.
The solvent is one or more of acetone, N-dimethylformamide and N, N-dimethylacetamide.
The end capping agent is one or a combination of a plurality of 2, 4-dihydroxyphenethylamine hydrochloride, dopamine hydrochloride and 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride.
The application of the antistatic self-repairing polyurethane material suitable for the marine environment in marine engineering, submarine tunnels, oil and gas transportation and submarine cable sea pipes.
The antistatic self-repairing polyurethane material which is obtained by the preparation method and is suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cable sea pipes.
The beneficial effects are that: compared with the prior art, the invention has the characteristics that:
(1) Acrylic acid is added into an isocyanate-polyethylene glycol system in advance, the dispersibility of the acrylic acid in a polyurethane system is improved by utilizing the actions of hydrogen bond and the like of the acrylic acid and polyethylene glycol monomers, meanwhile, the acrylic acid monomers and the acrylic acid hydroxy ester are copolymerized, the rapid self-polymerization behavior of the acrylic acid hydroxy ester added into a reaction system is effectively avoided, and the polymerization degree of acrylic acid copolymerization fragments is controlled. The obtained acrylic acid copolymer fragment has strong ion binding capacity and rich hydrogen bonds, and can further act with choline ion conductive agents to form a stable ion-polymer solid ion skeleton, salt conductive agents such as ferric chloride and the like are not needed, meanwhile, the structural stability is good, the dispersion is more uniform, the aggregation crystallization behavior of the salt conductive agents is avoided, and therefore, the antistatic performance of the polyurethane material is stable, the lower resistivity of the polyurethane is endowed, and the structural stability reaches 10 7 Omega.m level, and simultaneously, dynamic bonds such as hydrogen bonds, ionic bonds and the like provide self-repairing potential for polyurethane.
(2) By adding hydroxyl acrylate in stages and promoting the acrylic copolymer segment to react with pentaerythritol triacrylate, the polymerization degree of the acrylic acid-acrylic ester copolymer segment in the system and the dispersibility in the polyurethane system are regulated, so that a polyurethane and acrylic ester cross-linked structure is formed, and the physical properties and the stability of the polymer are improved.
(3) The polyurethane is blocked by using the blocking agent with the ortho-position phenolic hydroxyl, and can be complexed with metal ions to realize the self-repairing of the polyurethane, and the prepared polyurethane has stronger self-repairing capability in seawater because the seawater contains abundant metal ions, so that the defect of shorter service life of the polyurethane material in seawater is overcome, and the application range of the polyurethane is expanded.
The invention discloses an antistatic self-repairing device suitable for marine environmentA polyurethane composite material, a preparation method and application thereof. The antistatic self-repairing polyurethane material suitable for the marine environment consists of polyurethane acrylic resin, a blocking agent, an ion conductive agent, a solvent and an AIBN initiator according to mass ratio. The hydroxyl acrylate and polyurethane are subjected to block copolymerization to form a stable and controllable crosslinking structure, a large number of hydrogen bonds and ionic bonds contained in the acrylic acid-hydroxyl acrylate copolymerization segment are utilized to carry out double bonding with an ionic conductive agent, conductive ions are introduced, and the resistivity of the material is reduced to 10 7 Omega-m class; the capping agent containing the ortho-phenolic hydroxyl groups is used for capping, and the self-repairing capability of the material is endowed by utilizing a great amount of metal complex bonds existing in seawater, so that the self-repairing capability of the material in a marine environment is enhanced. The antistatic self-repairing polyurethane material suitable for the marine environment has excellent mechanical, self-repairing and antistatic properties, and has good application prospects in the fields of marine engineering, submarine tunnels, oil and gas transportation, submarine cables and submarine pipes and the like.
Drawings
FIG. 1 is a sample scanning electron microscope image of the present invention;
FIG. 2 is a graph of mechanical properties after multiple repairs in the self-repair performance test of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 110 parts by weight of hexamethylene diisocyanate, 70 parts by weight of polyethylene glycol with Mn of 3000 and 5 parts by weight of acrylic acid into a reaction kettle, and reacting for 50 minutes under the protection of nitrogen at 80 ℃ by using 0.3 part by weight of dibutyl tin laurate catalyst;
(2) Adding 50 parts by weight of hydroxypropyl methacrylate and 0.5 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 80 minutes at 60 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 200-250;
(3) Mixing 15 parts by weight of hydroxypropyl methacrylate, 2 parts by weight of pentaerythritol triacrylate, 15 parts by weight of polyether polyol and 80 parts by weight of N, N-dimethylacetamide, dropwise adding the mixture into the reaction liquid in the step (2) at the speed of 20 parts by weight/min, and reacting for 180 minutes under the condition of nitrogen protection at 100 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) 120 parts by weight of polyurethane acrylic resin prepolymer, 10 parts by weight of carbachol and 25 parts of acetylcholine chloride are added into a reaction kettle, heated to 100 ℃ and stirred for 3 hours;
(5) To the product of step (4), 20 parts by weight of 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride was added and stirred at 80℃for 3 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 120 parts by weight of a urethane acrylic prepolymer, 20 parts by weight of a capping agent (4- (3-aminopropyl) benzene-1, 2-diol hydrochloride), 35 parts by weight of an ion conducting agent (10 parts by weight of carbachol and 25 parts of acetylcholine chloride), 80 parts by weight of a solvent (N, N-dimethylacetamide) and 0.5 part by weight of an AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 2
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 90 parts by weight of hexamethylene diisocyanate, 60 parts by weight of polyethylene glycol with Mn of 2000 and 15 parts by weight of acrylic acid into a reaction kettle, and reacting for 40 minutes under the protection of nitrogen at 70 ℃ by using 0.2 part by weight of dibutyl tin laurate catalyst;
(2) Adding 40 parts by weight of hydroxypropyl methacrylate and 0.3 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 60 minutes at 70 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 200-250;
(3) Mixing 12 parts by weight of hydroxypropyl methacrylate, 2 parts by weight of pentaerythritol triacrylate, 12 parts by weight of polyether polyol and 70 parts by weight of acetone, dropwise adding the mixture into the reaction liquid in the step (2) at a speed of 15 parts by weight/min, and reacting for 165 minutes under the condition of nitrogen protection at 90 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) Adding 100 parts by weight of polyurethane acrylic resin prepolymer and 30 parts by weight of acetylcholine chloride into a reaction kettle, heating to 90 ℃, and stirring for 2 hours;
(5) To the product of step (4), 15 parts by weight of dopamine hydrochloride was added and stirred at 70℃for 2.5 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 100 parts by weight of polyurethane acrylic resin prepolymer, 15 parts by weight of a capping agent (dopamine hydrochloride), 30 parts by weight of an ion conducting agent (acetylcholine chloride), 70 parts by weight of a solvent (acetone) and 0.3 part by weight of AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 3
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 80 parts by weight of hexamethylene diisocyanate, 65 parts by weight of polyethylene glycol with Mn of 1500 and 5 parts by weight of acrylic acid into a reaction kettle, and reacting for 35 minutes under the protection of nitrogen at 65 ℃ by using 0.2 part by weight of dibutyl tin laurate catalyst;
(2) Adding 35 parts by weight of hydroxyethyl ethylacrylate and 0.3 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 120 minutes at 65 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 250-300;
(3) 13 parts by weight of hydroxyethyl ethylacrylate, 3 parts by weight of pentaerythritol triacrylate, 14 parts by weight of polyether polyol and 70 parts by weight of N, N-dimethylformamide are mixed, and are added into the reaction liquid in the step (2) dropwise at the speed of 14 parts by weight/min, and the mixture is reacted for 160 minutes under the condition of nitrogen protection at the temperature of 85 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) Adding 95 parts by weight of polyurethane acrylic resin prepolymer and 25 parts by weight of carbachol into a reaction kettle, heating to 85 ℃, and stirring for 1.5 hours;
(5) To the product of step (4), 18 parts by weight of 2, 4-dihydroxyphenethylamine hydrochloride was added, and stirred at 65℃for 2 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 95 parts by weight of a urethane acrylic prepolymer, 18 parts by weight of a capping agent (2, 4-dihydroxyphenethylamine hydrochloride), 25 parts by weight of an ion conducting agent (carbachol), 70 parts by weight of a solvent (N, N-dimethylformamide) and 0.3 part by weight of an AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 4
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 75 parts by weight of hexamethylene diisocyanate, 50 parts by weight of polyethylene glycol with Mn of 1000 and 20 parts by weight of acrylic acid into a reaction kettle, and reacting for 30 minutes under the protection of nitrogen at 60 ℃ by using 0.1 part by weight of dibutyl tin laurate catalyst;
(2) Adding 30 parts by weight of hydroxyethyl methacrylate and 0.2 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 120 minutes at 60 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 250-300;
(3) Mixing 10 parts by weight of hydroxyethyl methacrylate, 3 parts by weight of pentaerythritol triacrylate, 10 parts by weight of polyether polyol and 50 parts by weight of acetone, dropwise adding the mixture into the reaction liquid in the step (2) at the speed of 10 parts by weight/min, and reacting for 150 minutes under the condition of nitrogen protection at 80 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) Adding 80 parts by weight of polyurethane acrylic resin prepolymer and 20 parts by weight of choline chloride into a reaction kettle, heating to 80 ℃, and stirring for 1 hour;
(5) To the product of step (4), 10 parts by weight of 2, 4-dihydroxyphenethylamine hydrochloride was added, and stirred at 60℃for 2 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 180 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 80 parts by weight of polyurethane acrylic resin prepolymer, 10 parts by weight of a capping agent (2, 4-dihydroxyphenethylamine hydrochloride), 20 parts by weight of an ion conducting agent (choline chloride), 50 parts by weight of a solvent (acetone) and 0.2 part by weight of an AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 5
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 100 parts by weight of hexamethylene diisocyanate, 65 parts by weight of polyethylene glycol with Mn of 2500 and 5 parts by weight of acrylic acid into a reaction kettle, and reacting for 45 minutes under the condition of nitrogen protection at 75 ℃ by 0.3 part by weight of dibutyl tin laurate catalyst;
(2) Adding 45 parts by weight of hydroxyethyl ethylacrylate and 0.4 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 120 minutes at 80 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 300-400;
(3) Mixing 14 parts by weight of hydroxyethyl ethacrylate, 4 parts by weight of pentaerythritol triacrylate, 15 parts by weight of polyether polyol and 70 parts by weight of acetone, dropwise adding the mixture into the reaction liquid in the step (2) at a speed of 17 parts by weight/min, and reacting for 170 minutes under the protection of nitrogen at 90 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) Adding 100 parts by weight of polyurethane acrylic resin prepolymer and 20 parts by weight of carbachol into a reaction kettle, heating to 90 ℃, and stirring for 2 hours;
(5) To the product of step (4), 18 parts by weight of 2, 4-dihydroxyphenethylamine hydrochloride was added, and stirred at 75℃for 3 hours under nitrogen.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 180 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 100 parts by weight of polyurethane acrylic resin prepolymer, 18 parts by weight of a capping agent (2, 4-dihydroxyphenethylamine hydrochloride), 20 parts by weight of an ion conducting agent (carbachol), 70 parts by weight of a solvent (acetone) and 0.4 part by weight of an AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 6
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 110 parts by weight of hexamethylene diisocyanate, 70 parts by weight of polyethylene glycol with Mn of 3000 and 5 parts by weight of acrylic acid into a reaction kettle, and reacting for 50 minutes under the protection of nitrogen at 80 ℃ by using 0.3 part by weight of dibutyl tin laurate catalyst;
(2) Adding 50 parts by weight of hydroxypropyl methacrylate and 0.5 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 120 minutes at 80 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 300-400;
(3) Mixing 15 parts by weight of hydroxypropyl methacrylate, 3 parts by weight of pentaerythritol triacrylate, 15 parts by weight of polyether polyol and 80 parts by weight of N, N-dimethylacetamide, dropwise adding the mixture into the reaction liquid in the step (2) at the speed of 20 parts by weight/min, and reacting for 180 minutes under the condition of nitrogen protection at 100 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) 120 parts by weight of polyurethane acrylic resin prepolymer and 35 parts by weight of carbachol are added into a reaction kettle, heated to 100 ℃ and stirred for 3 hours;
(5) To the product of step (4), 20 parts by weight of 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride was added and stirred at 80℃for 3 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 120 parts by weight of a urethane acrylic prepolymer, 20 parts by weight of a capping agent (4- (3-aminopropyl) benzene-1, 2-diol hydrochloride), 35 parts by weight of an ion conducting agent (carbachol), 80 parts by weight of a solvent (N, N-dimethylacetamide) and 0.5 part by weight of AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Example 7
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 110 parts by weight of hexamethylene diisocyanate, 70 parts by weight of polyethylene glycol with Mn of 3000 and 5 parts by weight of acrylic acid into a reaction kettle, and reacting for 50 minutes under the protection of nitrogen at 80 ℃ by using 0.3 part by weight of dibutyl tin laurate catalyst;
(2) Adding 50 parts by weight of hydroxypropyl methacrylate and 0.5 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting for 120 minutes at 80 ℃ under the protection of nitrogen, wherein the average polymerization degree of acrylic monomers in the polymer is controlled to be 350-400;
(3) Mixing 15 parts by weight of hydroxypropyl methacrylate, 3 parts by weight of pentaerythritol triacrylate, 15 parts by weight of polyether polyol and 80 parts by weight of N, N-dimethylacetamide, dropwise adding the mixture into the reaction liquid in the step (2) at the speed of 20 parts by weight/min, and reacting for 180 minutes under the condition of nitrogen protection at 100 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) 120 parts by weight of polyurethane acrylic resin prepolymer and 35 parts of acetylcholine chloride are added into a reaction kettle, heated to 100 ℃ and stirred for 3 hours;
(5) To the product of step (4), 20 parts by weight of 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride was added and stirred at 80℃for 3 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 80 hours.
An antistatic self-repairing polyurethane material suitable for marine environment comprises the following components: 120 parts by weight of a urethane acrylic prepolymer, 20 parts by weight of a capping agent (4- (3-aminopropyl) benzene-1, 2-diol hydrochloride), 35 parts by weight of an ion conducting agent (acetylcholine chloride), 80 parts by weight of a solvent (N, N-dimethylacetamide) and 0.5 part by weight of an AIBN initiator.
The antistatic self-repairing polyurethane material suitable for the marine environment is applied to marine engineering, submarine tunnels, oil and gas transportation and submarine cables and submarine pipes.
Comparative example 1 (this comparative example was carried out without adding acrylic acid in step (1))
The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment comprises the following specific preparation steps:
(1) Adding 110 parts by weight of hexamethylene diisocyanate and 70 parts by weight of polyethylene glycol with Mn of 3000 into a reaction kettle, and reacting for 50 minutes under the protection of nitrogen at 80 ℃ by using 0.3 part by weight of dibutyl tin laurate catalyst;
(2) Adding 50 parts by weight of hydroxypropyl methacrylate and 0.5 part by weight of AIBN initiator into the reaction liquid in the step (1), and reacting at 60 ℃ under the protection of nitrogen, wherein the average polymerization degree of hydroxypropyl methacrylate monomers in the polymer is controlled to be 200-250;
(3) Mixing 15 parts by weight of hydroxypropyl methacrylate, 2 parts by weight of pentaerythritol triacrylate, 15 parts by weight of polyether polyol and 80 parts by weight of N, N-dimethylacetamide, dropwise adding the mixture into the reaction liquid in the step (2) at the speed of 20 parts by weight/min, and reacting for 180 minutes under the condition of nitrogen protection at 100 ℃ to obtain a polyurethane acrylic resin prepolymer;
(4) 120 parts by weight of polyurethane acrylic resin prepolymer, 10 parts by weight of carbachol and 25 parts of acetylcholine chloride are added into a reaction kettle, heated to 100 ℃ and stirred for 3 hours;
(5) To the product of step (4), 20 parts by weight of 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride was added and stirred at 80℃for 3 hours under nitrogen protection.
(6) Pouring the solution obtained in the step (5) into a mould, and drying at 160 ℃ for 60 hours.
An antistatic self-repairing polyurethane material suitable for marine environments prepared in example 1-example 7 and comparative example 1 was tested to obtain the following results:
(1) The mechanical properties of the materials were examined by an electronic universal tester, the tensile properties were tested according to the national standard GB528-2009, the tensile rate was 200mm/min, the tensile properties were measured by dumbbell-shaped bars, 25mm (length). Times.4 mm (width). Times.2 mm (thickness), and the tensile properties were measured as shown in Table 1 below.
TABLE 1 tensile Property test
The tensile test of examples 1-7 shows that as the polymerization degree of the acrylic monomer copolymer fragment increases, the tensile strength of the corresponding polyurethane gradually decreases and the elongation at break gradually increases; the main reason is that the acrylic ester is of a linear structure, and the content of the soft segment in the polyurethane is increased along with the increase of the content of the acrylic ester, so that the strength is reduced to some extent; the remaining examples show that by adjusting the content of the components, the polyurethane exhibits variable tensile strength and elongation at break, which can be adjusted in specific applications. As is clear from comparative example 1, the addition of acrylic acid has little effect on self-healing properties.
(2) Evaluation of antistatic Property volume resistivity was measured according to the test method of GB/T1410-2006 solid insulation volume resistivity and surface resistivity test method. The sample was prepared into a hollow tube having an inner diameter of 10cm, an outer diameter of 15cm and a length of 1m, the shape of the oil and gas transportation pipeline was simulated, and the volume resistivity thereof was measured, and the results are shown in Table 2 below.
TABLE 2 antistatic Performance test
The antistatic performance of the prepared polyurethane material is endowed by the choline ion conductive agent, and the more the consumption is, the lower the volume conductivity of the polyurethane is, and the stronger the antistatic capability is. Through antistatic tests of the examples 1-7, it is known that the introduction of the choline ion conductive agent into polyurethane can effectively improve the antistatic performance of polyurethane, and lays a foundation for further industrial application and antistatic polyurethane field. Comparative example 6 and comparative example 1 found that effective combination of choline ion conductive agent cannot be achieved without adding acrylic acid monomer in advance to participate in copolymerization of hydroxyl acrylate, resulting in uneven dispersion of ion conductive agent, remarkable improvement of surface resistivity and remarkable decrease of antistatic property. Therefore, the addition of the acrylic acid has no obvious influence on the tensile property of the antistatic agent, and mainly influences the dispersing effect of the antistatic agent on the choline antistatic agent, thereby influencing the antistatic property of the antistatic agent.
(3) Cutting off the sample by a knife, soaking in artificial seawater for 30 minutes to combine the sections, and the self-repairing material provided by the method does not need external force (such as heating, pressurizing and the like). The formula of the artificial seawater is as follows: 26.73g of sodium chloride, 2.26 g of g g of magnesium chloride, 3.25g of magnesium sulfate, 1.15g of calcium chloride, 0.20g of sodium bicarbonate, 0.72g of potassium chloride, 0.058g of sodium bromide, 0.058g of boric acid, 0.0024g of sodium silicate, 0.0015g of sodium silicate, 0.002g g of phosphoric acid, 0.013 g g of aluminum hexachloride, 0.002g of ammonia, 0.0013g of lithium nitrate and 1000g of water. Observing the sample by adopting a microscope, and characterizing the self-healing effect of the sample; the self-repairing rate is characterized by tensile property through an electronic universal tester, and the tensile rate is 50mm/min by referring to GB 528-2009. Taking the sample of example 2 as an example, a self-repairing effect graph (sample scanning electron microscope graph) is shown in fig. 1, and a mechanical property curve of the self-repairing in seawater for 4 times is shown in fig. 2: the self-repairing rate can be obtained by comparing the tensile breaking strength of the healed sample with the original strengthThe self-repairing rate calculation formula is as follows: self-repair rate = post-repair tensile strength/original tensile strength. The self-healing capacity test is shown in table 3.
TABLE 3 self-healing Capacity test
According to analysis of the embodiment, the polyurethane material synthesized by the method has certain self-repairing capability, and the self-repairing capability mainly depends on the synergistic effect of various dynamic bonds, including metal complex bonds in a polyurethane system, and the self-repairing capability of the material is promoted by hydroxyl acrylate endowing hydrogen bonds and ionic bonds.
As described above: the antistatic property of the antistatic self-repairing polyurethane material provided by the invention mainly comes from the introduction of an ionic conductive agent, and the self-repairing property mainly depends on the synergistic effect of various dynamic bonds, including metal complex bonds in a polyurethane system, hydroxyl acrylate endows hydrogen bonds, ionic bonds and the like. The preparation method has low cost, does not need to be additionally doped with conductive powder and antistatic agent, and the obtained polyurethane material has good mechanical properties, antistatic property, mechanical properties and good self-repairing property; the material composition and structure of the material are strong in controllability, and the material has good market application prospect.
While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of the above description, will appreciate that other embodiments are contemplated within the scope of the invention as described herein. Furthermore, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter. Accordingly, many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the appended claims. The disclosure of the present invention is intended to be illustrative, but not limiting, of the scope of the invention, which is defined by the appended claims.
Claims (5)
1. The preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment is characterized by comprising the following steps of:
(1) Adding 80-120 parts by weight of polyurethane acrylic resin prepolymer and 20-35 parts by weight of ionic conductive agent into a reaction kettle, heating to 80-100 ℃, and stirring for 1-3 hours;
(2) Adding 10-20 parts by weight of a blocking agent into the product of the step (1), and stirring for 2-3 hours at 60-80 ℃ under the protection of nitrogen to obtain a solution;
(3) Pouring the solution obtained in the step (2) into a mold, and drying for 60-80 hours at 160-180 ℃;
the preparation method of the polyurethane acrylic resin prepolymer comprises the following steps:
(01) Adding 75-110 parts by weight of hexamethylene diisocyanate, 50-70 parts by weight of polyethylene glycol with Mn of 1000-3000 and 5-20 parts by weight of acrylic acid into a reaction kettle, adding 0.1-0.3 part by weight of dibutyl tin laurate catalyst, and reacting for 30-50 minutes at 60-80 ℃ under the protection of nitrogen to obtain a first reaction solution;
(02) Adding 30-50 parts by weight of hydroxyl acrylate and 0.2-0.5 part by weight of AIBN initiator into the first reaction liquid in the step (01), reacting for 60-120 minutes at 60-80 ℃ under the protection of nitrogen, and controlling the average polymerization degree of acrylic monomers in the polymer to be 200-400 to obtain a second reaction liquid;
(03) Mixing 10-15 parts by weight of hydroxyl acrylate, 2-4 parts by weight of pentaerythritol triacrylate, 10-15 parts by weight of polyether polyol and 50-80 parts by weight of solvent, dropwise adding the mixture into the reaction liquid II in the step (02) at the speed of 10-20 parts by weight/min, and reacting for 150-180 minutes at the temperature of 80-100 ℃ under the protection of nitrogen to obtain a polyurethane acrylic resin prepolymer;
the ionic conductive agent is one or a combination of a plurality of choline chloride, acetylcholine chloride and carbachol;
the end capping agent is one or a combination of a plurality of 2, 4-dihydroxyphenethylamine hydrochloride, dopamine hydrochloride and 4- (3-aminopropyl) benzene-1, 2-diol hydrochloride.
2. The method according to claim 1, wherein the hydroxy acrylate is one or a combination of hydroxy ethyl methacrylate, hydroxy propyl methacrylate, and hydroxy ethyl ethacrylate.
3. The method of claim 1, wherein the solvent is a combination of one or more of acetone, N-dimethylformamide and N, N-dimethylacetamide.
4. The antistatic self-repairing polyurethane material suitable for the marine environment, which is obtained by the preparation method of the antistatic self-repairing polyurethane material suitable for the marine environment, is characterized by comprising the following components: 80-120 parts by weight of polyurethane acrylic resin prepolymer, 10-20 parts by weight of end capping agent, 20-35 parts by weight of ion conducting agent, 50-80 parts by weight of solvent and 0.2-0.5 part by weight of AIBN initiator.
5. The antistatic self-repairing polyurethane material suitable for marine environments according to claim 4, which is applied to marine engineering.
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